Pre-processing Bio-oil Before Hydrotreatment

ABSTRACT

Described are methods and systems for preparing stabilized bio-oil suitable for subsequent hydrotreatment and forming a hydrocarbon product from a stabilized bio-oil. For example, preparing stabilized bio-oil suitable for subsequent hydrotreatment may include filtering bio-oil effective to remove at least a portion of particles having an effective particulate diameter greater than about 10 micrometers; treating the bio-oil effective to remove at least a portion of inorganic species from the bio-oil; and catalytically stabilizing the bio-oil to provide the stabilized bio-oil suitable for subsequent hydrotreatment. Forming a hydrocarbon product from a stabilized bio-oil may include hydrotreating the stabilized bio-oil by, for example, contacting the stabilized bio-oil to a hydrotreatment catalyst in the presence of hydrogen, thereby providing the hydrocarbon product. Also included are stabilized bio-oil and hydrocarbon products derived therefrom.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Pat. App. No.62/129,007, filed on Mar. 5, 2015, and 62/245,423, filed Oct. 23, 2015,each of which is entirely incorporated by reference herein.

STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY-SPONSOREDRESEARCH AND DEVELOPMENT

This invention was made with Government support under Contract Nos.DE-AC0576RLO1830 and DE-EE0004391, awarded by the U.S. Department ofEnergy. The Government has certain rights in the invention.

BACKGROUND

Pyrolytic bio-oil derived from biomass may have limited commercialapplications because of poor heating value (˜17 MJ/kg), high oxygencontent (˜45 wt %), high viscosity (>200 cP), and corrosiveness. It ishighly desirable that such liquid hydrocarbon products produced frombio-oil be substantially reduced in water content, viscosity, andcorrosiveness in order to provide miscibility with petroleum-based fuelsand compatibility with petroleum refining unit operations.

Bio-oil may be hydrotreated using heterogeneous catalysts and may beused to produce improved liquid hydrocarbon products such as gasoline,kerosene, and diesel fractions. With existing technology, hydrotreatmentcatalysts may unfortunately become deactivated due to carbon depositionfrom bio-oil polymerization and coke formation, leading to a low “TimeOn Stream” (TOS) of a few hundred hours before a hydrotreatmentapparatus must be shut down for catalyst maintenance. This substantiallyincreases the cost of such operations and limits the rate and economicviability of liquid hydrocarbon products produced from bio-oil.

The lack of solutions in the art to these significant barriers havesubstantially limited the production viability of improved liquidhydrocarbon products from pyrolytic bio-oil. In recognition of theseissues, the U.S. Department of Energy has called for solutions, forexample, in “Upgrading of Biomass Fast Pyrolysis Oil (Bio-oil),” FundingOpportunity Announcement Number: DE-FOA-0000342, the entire contents ofwhich are incorporated herein by reference.

The present application appreciates that production of improved liquidhydrocarbon products from pyrolytic bio-oil may be a challengingendeavor.

SUMMARY

In one embodiment, a method for preparing stabilized bio-oil suitablefor subsequent hydrotreatment is provided. The method may includeproviding the bio-oil. The method may include filtering the bio-oileffective to remove at least a portion of particles having an effectiveparticulate diameter greater than about 10 micrometers. The method mayinclude treating the bio-oil effective to remove at least a portion ofinorganic species from the bio-oil. The method may include catalyticallystabilizing the bio-oil. The method may thereby provide the stabilizedbio-oil suitable for subsequent hydrotreatment.

In another embodiment, a method for forming a hydrocarbon product from astabilized bio-oil is provided. The method may include providing thestabilized bio-oil. The method may include hydrotreating the stabilizedbio-oil by thereby providing the hydrocarbon product.

In one embodiment, a system for forming a hydrocarbon product frombiomass is provided. The system may include a pyrolysis reactorconfigured to pyrolyze a biomass input and provide a bio-oil output. Thesystem may include an inline filter operatively coupled to receive thebio-oil output. The inline filter may be configured to remove at least aportion of particles having an effective diameter greater than about 10micrometers from the bio-oil output to provide a coarse-filtered bio-oiloutput. The system may include a fine filtration module configured toreceive the coarse-filtered bio-oil output. The fine filtration modulemay be configured to remove at least a portion of particles having aneffective diameter greater than about 5 micrometers to provide afine-filtered bio-oil output. The system may include a bed configured tocontain an ion exchange resin effective to receive the fine-filteredbio-oil. The bed may be configured to remove at least a portion ofinorganic species from the fine filtered bio-oil to produce areduced-inorganic bio-oil output. The system may include a firstcatalytic unit configured to contain a stabilizing catalyst effective toreceive the reduced-inorganic bio-oil. The first catalytic unit may beconfigured to stabilize the reduced-inorganic bio-oil to produce astabilized bio-oil output. The system may include a second catalyticunit configured to contain a hydrotreatment catalyst effective toreceive the stabilized bio-oil. The second catalytic unit may beconfigured to hydrotreat the stabilized bio-oil to provide a hydrocarbonoutput. The system may include a hydrogen source operatively coupled toprovide hydrogen to one or more of the first catalytic unit and thesecond catalytic unit.

In another embodiment, a method for forming a hydrocarbon product from abio-oil is provided. The method may include providing the bio-oil. Themethod may include filtering the bio-oil effective to remove at least aportion of particles having an effective particulate diameter greaterthan about 10 micrometers. The method may include treating the bio-oileffective to remove at least a portion of inorganic species from thebio-oil. The method may include catalytically stabilizing the bio-oil toprovide a stabilized bio-oil. The method may include hydrotreating thestabilized bio-oil comprising contacting the stabilized bio-oil to ahydrotreatment catalyst in the presence of hydrogen, thereby providingthe hydrocarbon product.

In another embodiment, a stabilized bio-oil is provided. The stabilizedbio-oil may be prepared according to any of the methods described hereinor prepared using any of the systems described herein.

In one embodiment, a stabilized bio-oil is provided. The stabilized biooil may be characterized by one or more of: a total acid number (TAN)value less than 100 mg KOH/g; a water content of at least about 17 wt.%; a hydrogen to carbon ratio greater than 1.4:1; and an averagepercentage of aldehyde and ketone groups of less than about 5%.

In another embodiment, a hydrocarbon product derived from bio-oil isprovided. The hydrocarbon product derived from bio-oil may be preparedaccording to any of the methods described herein or prepared using anyof the systems described herein.

In one embodiment, a hydrocarbon product derived from bio-oil isprovided. The hydrocarbon product may be characterized by one or more ofthe following. The hydrocarbon product may be characterized by one ormore percentages by weight of: about 24% paraffin, about 5.6% aromatics,about 8.6% naphthalenes, about 59% nC₅-C₆ alkanes, and about 2.4%olefins. The hydrocarbon product may be characterized by one or more of:a density in grams/mL of 0.78-0.86; a total sulfur weight percent ofless than 0.08%; a pour point in ° C. of less than about 20; a viscosityin cPs of less than 2; a hydrogen:carbon atomic ratio of about 1.5:1 toabout 2.2:1; and an energy value in mega Joules per kilogram of about 40to 45.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying figures, which are incorporated in and constitute apart of the specification, illustrate example methods and apparatuses,and are used merely to illustrate example embodiments.

FIG. 1 is a schematic depicting the preparation of stabilized bio-oiland hydrocarbon products derived therefrom.

FIG. 2 is a flow diagram of an example method 200 for preparing astabilized bio-oil.

FIG. 3A is a flow diagram of an example method 300 for preparing ahydrocarbon product.

FIG. 3B is a flow diagram of an example method 350 for preparing ahydrocarbon product.

FIG. 4 is a block diagram of an example for preparing a hydrocarbonproduct from biomass.

FIG. 5 is a table of ICP analyses of bio-oil and synthetic bio-oil.

FIG. 6A is a flow diagram illustrating hydrotreatment of syntheticbio-oil.

FIG. 6B is a table of conditions used in the hydrotreatment of syntheticbio-oil without inorganic additives.

FIG. 6C is a table of conditions used in the hydrotreatment of syntheticbio-oil without inorganic additives and results obtained at various timeintervals.

FIG. 6D is a graph illustrating the percentage volume of C2-C6hydrocarbon gases detected after hydrotreatment of synthetic bio-oilwithout inorganic additives relative to time on stream.

FIG. 6E is a graph illustrating the density of the product organic phaseobtained after hydrotreatment of synthetic bio-oils with and withoutinorganic additives relative to time on stream.

FIG. 6F is a graph illustrating the percentage of water in the productorganic phase obtained after hydrotreatment of synthetic bio-oils withand without inorganic additives relative to time on stream.

FIG. 6G is a graph illustrating the percentage volume of C2-C6hydrocarbon gases detected after hydrotreatment of synthetic bio-oilswith and without inorganic additives relative to time on stream.

FIG. 7 is a flow diagram illustrating hydrotreatment of pyrolysisbio-oil.

FIG. 8 is a table summarizing the results of thermogravimetricexperiments.

FIG. 9A is a transmission electron microscope (TEM) photo illustrating ametal particle size and metal dispersion of a fresh catalyst.

FIG. 9B is a transmission electron microscope (TEM) photo illustrating ametal particle size and metal dispersion of a spent catalyst.

FIG. 10 is a graph of ICP analyses of fresh and spent (post 500 h TOS)catalysts showing that deposition of inorganic contaminants such as Ca,Fe and S are associated with deactivated catalyst.

FIG. 11 is a table reporting the concentration of various inorganicspecies measured for the fine-filtered bio-oil before and after contactwith the polystyrene sulfonic acid ion exchange resin under variousconditions.

FIG. 12 is a table summarizing the conditions used in cycle 1.

FIG. 13 is a graph illustrating liquid and dry yield ratios ofstabilized bio-oil product/cleaned bio-oil feed.

FIG. 14 is a graph illustrating the pH of the stabilized bio-oil productversus time on stream.

FIG. 15 is graph illustrating the water content in the liquid phase asdetermined by the Karl Fisher method.

FIG. 16A is a graph illustrating the molar hydrogen/carbon ratio (H/C)of the stabilized bio-oil as function of time on stream.

FIG. 16B is a graph illustrating the Total Acidity Number, TAN (mgKOH/gram of sample) as a function of time on stream.

FIG. 17A is a graph illustrating the density of the hydrocarbon productof Zone II versus time on stream.

FIG. 17B is a graph illustrating the consumption of hydrogen versus timeon stream.

FIG. 18A is an image of overlay ¹H NMR spectra from about 6 ppm to 13ppm of fine-filtered bio-oil and reduced-inorganic bio-oil.

FIG. 18B is an image of overlay ¹H NMR spectra from 0 ppm to about 6 ppmof fine-filtered bio-oil and reduced-inorganic bio-oil.

FIG. 19A is an image of overlay ¹H NMR spectra from about 6 ppm to 13ppm of reduced inorganic bio-oil at TOS=0 h and stabilized bio-oil atTOS=55-60 h, 106-112 h, 242-252 h, and 312-324 h.

FIG. 19B is an image of overlay ¹H NMR spectra from 0 ppm to about 6 ppmof reduced inorganic bio-oil at TOS=0 h and stabilized bio-oil atTOS=55-60 h, 106-112 h, 242-252 h, and 312-324 h.

FIG. 20A is an image of overlay ¹H NMR spectra from about 6 ppm to 13ppm of reduced inorganic bio-oil at TOS=0 h and stabilized bio-oil atTOS=466-478 h, 502-514 h, 676-700 h, 773-797 h, 820-844 h, 916-940 h,and 964-1010 h.

FIG. 20B is an image of overlay ¹H NMR spectra from 0 ppm to about 6 ppmof reduced inorganic bio-oil at TOS=0 h and stabilized bio-oil atTOS=466-478 h, 502-514 h, 676-700 h, 773-797 h, 820-844 h, 916-940 h,and 964-1010 h.

DETAILED DESCRIPTION

Pyrolytic bio-oil, as produced, includes contaminants that may tend tofoul conventional methods and catalysts for hydrogenating and crackingbio-oil to form hydrocarbon products. Such contaminants may includeparticulates, e.g., of char and ash, as well as compounds includinginorganic atoms such as Al, Ca, Fe, K, Mg, Na, Si, and S. Suchcontaminants may arise from the source biomass, from pyrolysis, byleaching from components of pyrolysis systems, and the like. Asdescribed in the EXAMPLES, such contaminants were found to foul anddeactivate catalysts. Further, as described in the EXAMPLES, removal ofthese contaminants may tend to reduce fouling and catalyst deactivation,leading to benefits such as better catalyst performance, easier catalystregeneration, longer Time On Stream (TOS) operation, and the like. Inparticular, embodiments described herein lead to substantially improvedTOS values compared to the prior art.

Accordingly, FIG. 1 is an example reaction flow diagram 100 illustratingan overview of various aspects of embodiments detailed herein. Reactionflow diagram 100 shows that a pyrolytic bio-oil 102 may be directed intoa filtering step 104 that may produce a filtered bio-oil 106. Thefiltered bio-oil 106 may be cleaned of at least some inorganic speciesin an ion exchange process 108, followed by the output of a cleanedbio-oil 110 with reduced content of the inorganic species. The cleanedbio-oil 110, which may still contain sulfur species, may be subjected toa mild catalytic stabilization in a Zone I process 112 to produce astabilized bio-oil 114. The stabilized bio-oil 114, which may stillcontain sulfur species, may be further hydrotreated and cracked using ahydrotreatment catalyst, e.g., a sulfided catalyst in a Zone II process116, which may output a hydrocarbon fuel product 118.

FIG. 2 is a flow diagram illustrating an example method 200 forpreparing stabilized bio-oil for subsequent hydrotreatment. In variousembodiments, the method may include 202 providing the bio-oil. Themethod may include 204 filtering the bio-oil effective to remove atleast a portion of particles having an effective particulate diametergreater than about 10 micrometers. The method may include 206 treatingthe bio-oil effective to remove at least a portion of inorganic speciesfrom the bio-oil. The method may include 208 catalytically stabilizingthe bio-oil. The method may thereby provide the stabilized bio-oilsuitable for subsequent hydrotreatment.

In some embodiments, providing the bio-oil may include pyrolyzingbiomass to produce the bio-oil. Providing the bio-oil may includepyrolyzing biomass to produce the bio-oil. The biomass may besubstantially free of small or large biomass particulates. For example,the biomass may be characterized by a particulate diameter distributionof between about 0.5 millimeters and about 5 millimeters. The method mayinclude preparing the biomass prior to the pyrolyzing by selecting thebiomass in a particulate diameter distribution of between about 0.5millimeters and about 5 millimeters. Providing the bio-oil may includepyrolyzing biomass to produce the bio-oil at a temperature in ° C. ofbetween about one or more of: 400 to 600, 400 to 550, and 450 to 500,for example, 450-500° C.

In several embodiments, providing the bio-oil may include pyrolyzingbiomass to produce the bio-oil in a downflow reactor. For example,providing the bio-oil may include pyrolyzing the biomass in a downflowreactor to produce a bio-oil vapor. Filtering the bio-oil may includein-line filtering the bio-oil vapor produced by the pyrolysis effectiveto remove at least a portion of the particles having the effectiveparticulate diameter greater than about 10 micrometers. Further, forexample, providing the bio-oil may include pyrolyzing the biomass in adownflow reactor to produce a bio-oil vapor and condensing the bio-oilvapor to provide the bio-oil in condensed form. Filtering the bio-oilmay include in-line filtering the bio-oil in condensed form effective toremove at least a portion of the particles having the effectiveparticulate diameter greater than about 10 micrometers.

In various embodiments, filtering the bio-oil may include removing atleast a portion of the particles having an effective particulatediameter in micrometers greater than one or more of about: 5, 4, 3, 2.5,2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, and 0.1, for example,an effective particulate diameter greater than about 0.8 micrometers orgreater than about 0.2 micrometers. Filtering the bio-oil may include afirst filtering process effective to remove at least a portion of theparticles having an effective particulate diameter greater than about 10micrometers. Filtering the bio-oil may include a second filteringprocess effective to remove at least a portion of the particles havingan effective particulate diameter in micrometers greater than one ormore of about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4,0.3, 0.2, and 0.1, for example, an effective particulate diametergreater than about 0.8 micrometers or greater than about 0.2micrometers. Filtering the bio-oil may include a second filteringprocess conducted on the bio-oil offline from a pyrolysis process usedto provide the bio-oil. Filtering the bio-oil may include a secondfiltering process conducted using a pressure differential in pounds persquare inch (PSI) of at least about one or more of: 5, 10, 15, 20, 30,40, 50, 60, 70, 80, 90, 100, 125, 150, 175, and 200, for example, apressure differential of about 80 PSI. Filtering the bio-oil may includea second filtering process conducted at a temperature in ° C. of atleast about one or more of: 30, 40, 50, 60, 70, 80, 90, and 100, forexample, at least about 40° C. or at least about 80° C.

In some embodiments, treating the bio-oil effective to remove at least aportion of inorganic species from the bio-oil may include contacting thebio-oil to one or more of: an ion exchange resin, a zeolite, andactivated carbon. The ion exchange resin may include any ion exchangeresin described herein. The zeolite may include any zeolite describedherein. For example, treating the bio-oil effective to remove at least aportion of inorganic species from the bio-oil may include contacting thebio-oil to an ion exchange resin in a fixed-bed column reactor or aslurry bed reactor. For example, the fixed-bed column reactor may beoperated in intermittent or continuous flow mode. For example, theslurry bed reactor may be operated in batch mode. Treating the bio-oileffective to remove at least a portion of inorganic species from thebio-oil may include contacting the bio-oil to an ion exchange resin at apressure in pounds per square inch gauge (PSIG) of about one or more of:0 to 100, 10 to 100, 10 to 75, 10 to 50, 10 to 25, and 10 to 20.Treating the bio-oil effective to remove at least a portion of inorganicspecies from the bio-oil may include contacting the bio-oil to an ionexchange resin at a temperature in ° C. of about one or more of: 25 to100, 25 to 75, 30 to 50, 35 to 45, and 40, for example, 40° C.

Suitable ion-exchange resins may include strongly acidic cation-exchangeresins. The ion exchange resin may be used in protonated form, forexample, including active SO₃H groups or CO₂H groups. Neutralizedsulfonic acid resins, in which some or all of the protons have beenexchanged by a cation such as lithium, sodium, potassium, magnesium, andcalcium may also be suitable. Resins having a counterion (i.e., sodium,Na+), may be converted to protonated form by treatment with aqueousacid, e.g., hydrochloric acid, nitric acid, sulfuric acid, substitutedsulfonic acids such as p-toluene sulfonic acid, and the like. This iscommonly known in the art as ion-exchange resin activation. The ionexchange resin may include sulfonated or carboxylated polymers orcopolymers of styrene. For example, the ion exchange resin may includeone or more of: a poly(styrene sulfonic acid), a poly(styrene carboxylicacid), and a poly(2-acrylamido-2-methyl-1-propanesulfonic acid).

Example ion exchange resins may include macroreticular resins. As usedherein, “macroreticular resins” may include two continuous phases—acontinuous pore phase and a continuous gel polymeric phase. Thecontinuous gel polymeric phase may be structurally composed of smallspherical microgel particles agglomerated together to form clusters thatmay form interconnecting pores. The surface area may correspond to theexposed surface of the microgel clusters. Macroreticular ion exchangeresins may be made with different surface areas ranging from 7 to 1500m²/g, and average pore diameters ranging from about 5 to about 10000 nm.

Example ion exchange resins may include gel-type resins. “Gel-typeresins” may be translucent. Gel-type resins may lack permanent porestructures. Gel-type resins may include molecular-scale micropores. Thepore structures may be determined by the distance between the polymerchains and crosslinks that may vary with the crosslink level of thepolymer, the polarity of the solvent, and the operating conditions.Macroreticular resins may be used for continuous column flow processeswhere minimization of resin swelling/shrinking may be desirable.Gel-type resins may be used for slurry bed batch processes.Macroreticular resins and gel-type resins may be used in eithercontinuous column flow or slurry bed batch processes.

Suitable ion-exchange resins may include those provided by Dow ChemicalCo., Midland, Mich. under the tradenames/trademarks DOWEX® MARATHON C,DOWEX® MONOSPHERE C-350, DOWEX® HCR-S/S, DOWEX® MARATHON MSC, DOWEX®MONOSPHERE 650C, DOWEX® HCR-W2, DOWEX® MSC-1, DOWEX® HGR NG (H), DOWE®DR-G8, DOWEX® 88, DOWEX® MONOSPHERE 88, DOWEX® MONOSPHERE C-600 B,DOWEX® MONOSPHERE M-31, DOWEX® MONOSPHERE DR-2030, DOWEX® M-31, DOWEX®G-26 (H), DOWEX® 50W-X4, DOWEX® 50W-X8, DOWEX® 66, AMBERLYST™ 131,AMBERLYST™ 15, AMBERLYST™ 16, AMBERLYST™ 31, AMBERLYST™ 33, AMBERLYST™35, AMBERLYST™ 36, AMBERLYST™ 39, AMBERLYST™ 40 AMBERLYST™ 70,AMBERLITE™ FPC11, AMBERLITE™ FPC22, AMBERLITE™ FPC23, and the like.Suitable ion-exchange resins may include those provided by BrotechCorp., Bala Cynwyd, Pa. (USA) under the trade names/trademarks PUROFINE®PFC150, PUROLITE® C145, PUROLITE® C150, PUROLITE® C160, PUROFINE®PFC100,PUROLITE® C100, and the like. Suitable ion-exchange resins may includethose provided by Thermax Limited Corp., Novi, Mich. under thetradename/trademark MONOPLUS™. 5100, TULUSION® T42, and the like.

For example, the poly(styrene sulfonic acid) may be characterized by oneor more of: a surface area of about 28 to 37 square meters per gram, aparticle diameter of 0.60 to 0.850 millimeters, a particle diameteruniformity coefficient of less than about 1.6, a total pore volume of0.15 to 0.25 milliliters per gram, an average pore diameter of about 200to 280 angstroms, and an exchange capacity of at least about 5milli-equivalents per gram.

In several embodiments, the inorganic species may include one or moreof: Al, Ca, Na, K, Mg, Fe, P, Si, S, and Zn. Treating the bio-oileffective to remove at least a portion of inorganic species from thebio-oil may include reducing the amount of one or more inorganic speciesin the bio-oil to a concentration in parts per million (ppm) of lessthan one or more of about: 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, and1, for example, less than about 6 ppm or less than about 3 ppm. Forexample, treating the bio-oil effective to remove at least a portion ofinorganic species from the bio-oil may include reducing a content oramount of one or more of, or each of: Al, Ca, Na, K, Mg, and Fe in thebio-oil to a corresponding concentration in ppm of less than one or moreof about: 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1, for example, less thanabout 6 ppm or less than about 3 ppm.

In various embodiments, catalytically stabilizing the bio-oil mayinclude contacting the bio-oil to a stabilizing catalyst. Thestabilizing catalyst may include a metal dispersed on a solid support,e.g., a metal oxide, a zeolite, carbon, and the like. The metaldispersed on a solid support may be acidic. For example, the metal mayinclude one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os.The metal oxide may include one or more of: titania, ceria, magnesiumoxide, niobium oxide, alumina, amorphous silica alumina, zirconia, zincoxide, niobic acid, tungstic acid, molybdic acid, carbon, and silica.

The method may include contacting the bio-oil to a diluting medium toform a diluted bio-oil. The method may include diluting the bio-oil inan organic solvent to form a diluted bio-oil. The organic solvent mayinclude a protic organic solvent, e.g., an alcohol. The organic solventmay include an aprotic organic solvent. The organic solvent may includea polar solvent. The organic solvent may include a polar protic solvent.The organic solvent may include a polar aprotic solvent. The organicsolvent may include a nonpolar solvent. The diluting medium may includean organic solvent including one or more of: a protic solvent, anaprotic solvent, a polar solvent, and a nonpolar solvent. The dilutingmedium may include an organic solvent including one or more of:methanol, ethanol, 2-propanol, n-butanol, sec-butanol, tert-butanol,pentanol, hexanol, methyl cyclohexanol, acetone, methyl ethyl ketone,butanone, ethyl acetate, tetrahydrofuran, methyl tert-butyl ether,diethyl ether, acetonitrile, dimethyl formamide, dimethylsulfoxide, andthe like. The method may include diluting the bio-oil in a petroleumfuel to form a diluted bio-oil. The petroleum fuel may include one ormore of: diesel, gasoline, kerosene, jet fuel, fuel oil, naptha,fractions thereof, combinations thereof, and the like. The method mayinclude diluting the bio-oil in a portion of the stabilized bio-oil toform the diluted bio-oil. The portion of the stabilized bio-oil mayinclude a light phase. The light phase may include water. The portion ofthe stabilized bio-oil may include a heavy phase. The heavy phase mayinclude the bio-oil. The portion of the stabilized bio-oil may includeone or more of: the light phase and the heavy phase. The method mayinclude diluting the bio-oil to form the diluted bio-oil in one or moreof: an organic solvent, a petroleum fuel, water, and a portion of thestabilized bio-oil.

The method may include diluting the bio-oil in a diluting medium to forma diluted bio-oil. Diluting the bio-oil in the diluting medium mayinclude diluting the bio-oil to a percentage by weight of the dilutingmedium of about one or more of: 5 to 50, 10 to 45, 15 to 40, 20 to 35,25 to 35, and 30.

The method may include contacting the bio-oil to a diluting medium toform a diluted bio-oil using a positive pressure differential in poundsper square inch compared to atmospheric pressure of at least about oneor more of: 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150,175, 200, 500, 1000, 1500, 1800, and 2000.

The method may include contacting the bio-oil to a diluting medium toform a diluted bio-oil and catalytically stabilizing the bio-oil.Catalytically stabilizing the bio-oil may include contacting the dilutedbio-oil to the stabilizing catalyst.

The method may include removing at least a portion of the dilutingmedium from the diluted bio-oil after catalytically stabilizing thediluted bio-oil. The diluting medium may include one or more of: theorganic solvent, the petroleum fuel, and the water. The removed dilutingmedium may be recycled.

In some embodiments, catalytically stabilizing the bio-oil may includecontacting the bio-oil to a stabilizing catalyst that includes azeolite. Further, the solid support may be a zeolite, e.g., an acidiczeolite. The zeolite may include one or more of: a Y zeolite, a Betazeolite, a ZSM-5 zeolite, a Mordenite zeolite, a Ferrierite zeolite, aAl-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22 zeolite, a SAPO-34zeolite, and a Chabazite zeolite.

In various embodiments, the stabilizing catalyst may include the metaldispersed on an acidic metal oxide, For example, the stabilizingcatalyst may include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni,Nb, and Os; dispersed on one or more of: titania, ceria, magnesiumoxide, niobium oxide, alumina, amorphous silica alumina, zirconia, zincoxide, niobic acid, tungstic acid, molybdic acid, carbon, and silica.For example, catalytically stabilizing the bio-oil may includecontacting the bio-oil to a stabilizing catalyst including Ru/TiO₂.

In some embodiments, the stabilizing catalyst may include the metaldispersed on an acidic zeolite. For example, the stabilizing catalystmay include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, andOs; dispersed on one or more of: a Y zeolite, a Beta zeolite, a ZSM-5zeolite, a Mordenite zeolite, a Ferrierite zeolite, a Al-MCM-41 zeolite,a MCM-48 zeolite, a MCM-22 zeolite, a SAPO-34 zeolite, and a Chabazitezeolite.

In several embodiments, catalytically stabilizing the bio-oil mayinclude contacting the bio-oil to a stabilizing catalyst at atemperature in ° C. of about one or more of: 40 to 300, 100 to 280, 120to 270, 130 to 250, 140 to 225, 150 to 200, 160 to 180, and 170.Catalytically stabilizing the bio-oil may include contacting the bio-oilto a stabilizing catalyst at a pressure in PSI of about one or more of:500 to 2500, 750 to 2250, 1000 to 2000, 1250 to 1750, 1400 to 1600, and1500. Catalytically stabilizing the bio-oil may include contacting thebio-oil to a stabilizing catalyst in the presence of hydrogen.Catalytically stabilizing the bio-oil may include providing asubstantial excess of hydrogen at a pressure in pounds per square inchgauge of one or more of: 100 to 2000, 500 to 1800, and 1000 to 1500.Catalytically stabilizing the bio-oil may include flowing the bio-oilpast a stabilizing catalyst at a liquid hourly space velocity (LHSV) ofbetween about 0.05 hr⁻¹ to 1 hr⁻¹. Catalytically stabilizing the bio-oilmay include contacting the bio-oil to a stabilizing catalyst for a TimeOn Stream (TOS) in hours of at least about one or more of: 200, 300,400, 500, 600, 700, 800, 900, 1000, 1,100, 1,200, 1,300, 1,400, 1,500,1,750, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and16,000.

In several embodiments, the method may include regenerating thestabilizing catalyst, for example, by rinsing the stabilizing catalystwith an organic solvent. The organic solvent may include a proticorganic solvent, e.g., an alcohol. The organic solvent may include oneor more of: methanol, ethanol, 2-propanol, n-butanol, sec-butanol,tert-butanol, pentanol, hexanol, methyl cyclohexanol, acetone, methylethyl ketone, butanone, ethyl acetate, tetrahydrofuran, methyltert-butyl ether, acetonitrile, and dimethyl formamide. The method mayinclude regenerating the stabilizing catalyst by contacting thestabilizing catalyst with hydrogen at a temperature in ° C. of about oneor more of: 250 to 550, 300 to 500, 325 to 475, 350 to 450, 375 to 425,and 400. For example, the hydrogen may chemically reduce carbonaccumulation on the stabilizing catalyst to produce gaseous methane.Such reducing may be desirable compared to oxidative methods of removingcarbon, because hydrogen reduction of carbon to methane may be lessexothermic than carbon oxidation in the presence of oxygen, leading toless heating and less thermal damage to the stabilizing catalyst, e.g.,by sintering.

In various embodiments, the stabilized bio-oil may be characterizedcompared to the bio-oil. For example, the stabilized bio-oil may becharacterized compared to the bio-oil by a decreased content ofaldehydes and free carboxylic acids. The stabilized bio-oil may becharacterized compared to the bio-oil by an increase in pH of at leastone or more of about: 0.25, 0.5, 0.75, 1, 1.25, and 1.5. The stabilizedbio-oil may be characterized compared to the bio-oil by a percentincrease in dry hydrogen:carbon ratio of one or more of about: 5, 10,15, 20, and 25. The stabilized bio-oil may be characterized compared tothe bio-oil by one or more of the characteristics recited in thisparagraph.

In some embodiments, the bio-oil may be characterized by one or more of:a density of about 1 to 1.2 grams per milliliter, a dry hydrogen:carbonratio of about 1.4:1, a dry oxygen weight percentage of about 20% to35%, and a water weight percentage of about 30% to 45%. The stabilizedbio-oil may be characterized by one or more of: a density of about 1 to1.1 grams per milliliter, a dry hydrogen:carbon ratio of about 1.2:1 to1.8:1, a dry oxygen weight percentage of about 20% to 35%, and a waterweight percentage of about 20% to 35%.

In several embodiments, the method may include cooling the stabilizedbio-oil prior to the subsequent hydrotreatment, insulating thestabilizing catalyst from heat of the subsequent hydrotreatment, orcooling the stabilizing catalyst against heat of the subsequenthydrotreatment.

The method may include conveying the stabilized bio-oil directly fromthe catalytically stabilizing to the subsequent hydrotreatment, forexample, as a continuous process.

The method may include a stabilized bio-oil including one or more of: alight phase and a heavy phase. The method may include feeding at leastthe heavy phase directly from the catalytically stabilizing to thesubsequent hydrotreatment. The method may include separating the lightphase from the heavy phase and feeding the heavy phase to the subsequenthydrotreatment. The method may include feeding the light phase and theheavy phase in parallel to the subsequent hydrotreatment. The method mayinclude controlling a ratio between the light phase and the heavy phaseand feeding the ratio of the light phase and the heavy phase in parallelto the subsequent hydrotreatment. The light phase:heavy phase mayinclude a ratio between about 1:20 and about 20:1.

The method may include conducting at least a portion of the method underan inert atmosphere. The inert atmosphere may include one or more of:nitrogen, carbon dioxide, and a non-condensable gas product of biomasspyrolysis.

FIGS. 3A and 3B are flow diagrams illustrating methods of forming ahydrocarbon product. For example, FIG. 3A is a flow diagram illustratingan example method 300 for forming a hydrocarbon product from astabilized bio-oil. In various embodiments, the method may include 302providing the stabilized bio-oil. The method may include 304hydrotreating the stabilized bio-oil by, for example, contacting thestabilized bio-oil to a hydrotreatment catalyst in the presence ofhydrogen, thereby providing the hydrocarbon product. Further, forexample, FIG. 3B is a flow diagram illustrating an example method 350for forming a hydrocarbon product from a bio-oil. In variousembodiments, the method may include 352 providing the bio-oil. Themethod may include 354 filtering the bio-oil effective to remove atleast a portion of particles having an effective particulate diametergreater than about 10 micrometers. The method may include 356 treatingthe bio-oil effective to remove at least a portion of inorganic speciesfrom the bio-oil. The method may include 358 catalytically stabilizingthe bio-oil to provide a stabilized bio-oil. The method may include 360hydrotreating the stabilized bio-oil comprising contacting thestabilized bio-oil to a hydrotreatment catalyst in the presence ofhydrogen, thereby providing the hydrocarbon product. Methods 300 and 350may incorporate of the following aspects.

For example, the stabilized bio-oil may be characterized by one or moreof: a total acid number (TAN) value less than 100 mg KOH/g; a watercontent of at least about 17 wt. %; a hydrogen to carbon ratio greaterthan 1.4:1; and an average percentage of aldehyde and ketone groups ofless than about 5%. The TAN may be, for example, a value in milligramsof potassium hydroxide per gram of less than one or more of: 100, 90,80, 70, 60, 50, 40, and 35. The water content may be, for example, apercent by weight of one or more of: 17 to 35, 20 to 35, 20 to 30, and25 to 30. The hydrogen:carbon ratio may be, for example, one or more of:1.4:1 to 1.9:1, 1.5:1 to 1.9:1, 1.6:1 to 1.9:1, 1.7:1 to 1.9:1, 1.4:1 to1.8:1, 1.6:1 to 1.8:1, and 1.7:1 to 1.8:1. The average percentage ofaldehyde and ketone groups, e.g., as measured by ¹H NMR may be a weightpercentage of one or more of: less than about 5%, less than about 4.5%,less than about 4%, less than about 3.5%, between about 1.5% and about3.5%, and between about 2% and about 3%.

In some embodiments, hydrotreating the stabilized bio-oil may includecontacting the stabilized bio-oil to the hydrotreatment catalyst in thepresence of hydrogen at a temperature in ° C. of about one or more of:200 to 420, 220 to 400, 240 to 380, 260 to 360, 280 to 340, 300 to 320,and 310. Hydrotreating the stabilized bio-oil may include contacting thestabilized bio-oil to the hydrotreatment catalyst at a pressure in PSIof about one or more of: 500 to 2500, 750 to 2250, 1000 to 2000, 1250 to1750, 1400 to 1600, and 1500.

In various embodiments, the hydrotreatment catalyst may be an activemetal catalyst or a sulfided catalyst.

For example, the active metal catalyst may include a metal dispersed ona solid support, e.g., a metal oxide, a zeolite, carbon, and the like,each of which may be acidic. For example, the metal may include one ormore of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The metal oxidemay include one or more of: titania, ceria, magnesium oxide, niobiumoxide, alumina, amorphous silica alumina, zirconia, zinc oxide, niobicacid, tungstic acid, molybdic acid, carbon, and silica. Thehydrotreatment catalyst may include a zeolite. Further, the solidsupport may be a zeolite, e.g., an acidic zeolite. The zeolite mayinclude one or more of: a Y zeolite, a Beta zeolite, a ZSM-5 zeolite, aMordenite zeolite, a Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48zeolite, a MCM-22 zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.

In various embodiments, the hydrotreatment catalyst may include themetal dispersed on an acidic metal oxide, For example, thehydrotreatment catalyst may include a metal including one or more of:Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The metal may bedispersed on a solid support comprising one or more of: titania, ceria,magnesium oxide, niobium oxide, alumina, amorphous silica alumina,zirconia, zinc oxide, niobic acid, tungstic acid, molybdic acid, carbon,silica, a Y zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenitezeolite, a Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, aMCM-22 zeolite, a SAPO-34 zeolite, a Chabazite zeolite, and carbon. Forexample, the active metal catalyst may include one or more of Ru/TiO₂,Ru/TiO₂—ZSM5 Pd/C, Pd/SiO₂—Al₂O₃, Pd/Nb/Al₂O₃, Pd/Nb/TiO₂—SiO₂,Pt/ZrO₂—Al₂O₃, and Pd/Mg/Al₂O₃.

Further, for example, the hydrotreatment catalyst may include a sulfidedcatalyst, e.g., including one or more of: Ni, Nb, Mo, Co, and W. Forexample, the sulfided catalyst may include one or more of sulfided: Ni,Nb, Mo, Co, W, NiMo, and CoMo.

In some embodiment, hydrotreating the stabilized bio-oil may includecontacting the stabilized bio-oil to the hydrotreatment catalyst in thepresence of a substantial excess of hydrogen at a pressure in pounds persquare inch gauge of one or more of: 100 to 2000, 500 to 1800, and 1000to 1500. Hydrotreating the stabilized bio-oil may include contacting thestabilized bio-oil to the hydrotreatment catalyst at a liquid hourlyspace velocity (LHSV) of between about 0.05 hr¹ to 1 hr⁻¹. Hydrotreatingthe stabilized bio-oil may include contacting the stabilized bio-oil tothe hydrotreatment catalyst in the presence of hydrogen for a TOS inhours of at least about one or more of: 200, 300, 400, 500, 600, 700,800, 900, 1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000,4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and 16,000.

In several embodiments, the hydrocarbon product may include a liquidfraction characterized compared to the stabilized bio-oil at 25° C. and1 atmosphere. The liquid fraction may be characterized compared to thestabilized bio-oil by one or more percentages by weight of: about 24%paraffin, about 5.6% aromatics, about 8.6% naphthalenes, about 59%nC₅-C₆ alkanes, and about 2.4% olefins. The liquid fraction may becharacterized compared to the stabilized bio-oil by one or more of: adensity in grams/mL of 0.78-0.86; a total sulfur weight percent of lessthan 0.08%, or less than about 0.01%; a pour point in ° C. of less thanabout 20; a viscosity in cPs of less than 2; a hydrogen:carbon atomicratio of about 1.5:1 to about 2.2:1, e.g., about 2.1:1; and an energyvalue in mega Joules per kilogram of about 40 to 45 or about 41 to 44 .. . . The liquid fraction may be characterized compared to thestabilized bio-oil by one or more of the characteristics described inthis paragraph.

In various embodiments, the hydrocarbon product may include a C₁-C₄ gasfraction, e.g., one or more of methane, ethane, propane, butane, and thelike. The hydrocarbon product may include a liquid fractioncharacterized by one or more of: a density of about 0.8 to about 0.86grams per milliliter, a hydrogen:carbon ratio of about 1.5:1 to about2.2:1, a dry oxygen weight percentage of about 0% to about 5%, e.g.,less than about 0.5%, and a water weight percentage of about 0% to about5%, e.g., less than about 0.5%.

In some embodiments, the method may include conducting at least aportion of the method under an inert atmosphere. The inert atmospheremay include one or more of: nitrogen, carbon dioxide, and anon-condensable gas product of biomass pyrolysis.

In several embodiments, providing the stabilized bio-oil may include:providing a bio-oil; filtering the bio-oil effective to remove at leasta portion of particles having an effective particulate diameter greaterthan about 10 micrometers; treating the bio-oil effective to remove atleast a portion of inorganic species from the bio-oil; and catalyticallystabilizing the bio-oil, thereby providing the stabilized bio-oil.

The method may include one or more of: cooling the stabilized bio-oilprior to hydrotreating the stabilized bio-oil, insulating thestabilizing catalyst from heat of hydrotreating the stabilized bio-oil,and cooling the stabilizing catalyst against heat of hydrotreating thestabilized bio-oil. The method may include conveying the stabilizedbio-oil directly from the catalytically stabilizing to thehydrotreating.

The method may include a stabilized bio-oil including one or more of: alight phase and a heavy phase. The method may include feeding at leastthe heavy phase directly from the catalytically stabilizing to thehydrotreating. The method may include separating the light phase fromthe heavy phase and feeding the heavy phase to the hydrotreating. Themethod may include feeding the light phase and the heavy phase inparallel to the hydrotreating. The method may include controlling aratio between the light phase and the heavy phase and feeding the ratioof the light phase and the heavy phase in parallel to the hydrotreating.The light phase:heavy phase may include a ratio between about 1:20 andabout 20:1.

In some embodiments, providing the bio-oil may include pyrolyzingbiomass to produce the bio-oil. Providing the bio-oil may includepyrolyzing biomass to produce the bio-oil. The biomass may besubstantially free of small or large biomass particulates. For example,the biomass may be characterized by a particulate diameter distributionof between about 0.5 millimeters and about 5 millimeters. The method mayinclude preparing the biomass prior to the pyrolyzing by selecting thebiomass in a particulate diameter distribution of between about 0.5millimeters and about 5 millimeters. Providing the bio-oil may includepyrolyzing biomass to produce the bio-oil at a temperature in ° C. ofbetween about one or more of: 400 to 600, 400 to 550, and 450 to 500,for example, 450-500° C.

In several embodiments, providing the bio-oil may include pyrolyzingbiomass to produce the bio-oil in a downflow reactor. For example,providing the bio-oil may include pyrolyzing the biomass in a downflowreactor to produce a bio-oil vapor. Filtering the bio-oil may includein-line filtering the bio-oil vapor produced by the pyrolysis effectiveto remove at least a portion of the particles having the effectiveparticulate diameter greater than about 10 micrometers. Further, forexample, providing the bio-oil may include pyrolyzing the biomass in adownflow reactor to produce a bio-oil vapor and condensing the bio-oilvapor to provide the bio-oil in condensed form. Filtering the bio-oilmay include in-line filtering the bio-oil in condensed form effective toremove at least a portion of the particles having the effectiveparticulate diameter greater than about 10 micrometers.

In various embodiments, filtering the bio-oil may include removing atleast a portion of the particles having an effective particulatediameter in micrometers greater than one or more of about: 5, 4, 3, 2.5,2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, and 0.1, for example,an effective particulate diameter greater than about 0.8 micrometers orgreater than about 0.2 micrometers. Filtering the bio-oil may include afirst filtering process effective to remove at least a portion of theparticles having an effective particulate diameter greater than about 10micrometers. Filtering the bio-oil may include a second filteringprocess effective to remove at least a portion of the particles havingan effective particulate diameter in micrometers greater than one ormore of about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4,0.3, 0.2, and 0.1, for example, an effective particulate diametergreater than about 0.8 micrometers or greater than about 0.2micrometers. Filtering the bio-oil may include a second filteringprocess conducted on the bio-oil offline from a pyrolysis process usedto provide the bio-oil. Filtering the bio-oil may include a secondfiltering process conducted using a pressure differential in pounds persquare inch (PSI) of at least about one or more of: 5, 10, 15, 20, 30,40, 50, 60, 70, 80, 90, 100, 125, 150, 175, and 200, for example, apressure differential of about 80 PSI. Filtering the bio-oil may includea second filtering process conducted at a temperature in ° C. of atleast about one or more of: 30, 40, 50, 60, 70, 80, 90, and 100, forexample, at least about 40° C. or at least about 80° C.

In some embodiments, treating the bio-oil effective to remove at least aportion of inorganic species from the bio-oil may include contacting thebio-oil to one or more of: an ion exchange resin, a zeolite, andactivated carbon. The ion exchange resin may include any ion exchangeresin described herein. The zeolite may include any zeolite describedherein. For example, treating the bio-oil effective to remove at least aportion of inorganic species from the bio-oil may include contacting thebio-oil to an ion exchange resin in a fixed-bed column reactor or aslurry bed reactor. For example, the fixed-bed column reactor may beoperated in intermittent or continuous flow mode, and the slurry bedreactor may be operated in batch mode. Treating the bio-oil effective toremove at least a portion of inorganic species from the bio-oil mayinclude contacting the bio-oil to an ion exchange resin at a pressure inpounds per square inch gauge (PSIG) of about one or more of: 0 to 100,10 to 100, 10 to 75, 10 to 50, 10 to 25, and 10 to 20. Treating thebio-oil effective to remove at least a portion of inorganic species fromthe bio-oil may include contacting the bio-oil to an ion exchange resinat a temperature in ° C. of about one or more of: 25 to 100, 25 to 75,30 to 50, 35 to 45, and 40, for example, 40° C. The ion exchange resinmay include one or more of: a poly(styrene sulfonic acid), apoly(styrene carboxylic acid), and apoly(2-acrylamido-2-methyl-1-propanesulfonic acid). For example, thepoly(styrene sulfonic acid) may be characterized by one or more of: asurface area of about 28 to 37 square meters per gram, a particlediameter of 0.60 to 0.850 millimeters, a particle diameter uniformitycoefficient of less than about 1.6, a total pore volume of 0.15 to 0.25milliliters per gram, an average pore diameter of about 200 to 280angstroms, and an exchange capacity of at least about 5 milliequivalentsper gram

In several embodiments, the inorganic species may include one or moreof: Al, Ca, Na, K, Mg, Fe, P, Si, S, and Zn. Treating the bio-oileffective to remove at least a portion of inorganic species from thebio-oil may include reducing one or more inorganic species in thebio-oil to a concentration in parts per million (ppm) of less than oneor more of about: 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1, forexample, less than about 6 ppm or less than about 3 ppm. For example,treating the bio-oil effective to remove at least a portion of inorganicspecies from the bio-oil may include reducing a content of one or moreof, or each of: Al, Ca, Na, K, Mg, and Fe in the bio-oil to acorresponding concentration in ppm of less than one or more of about:10, 9, 8, 7, 6, 5, 4, 3, 2, and 1, for example, less than about 6 ppm orless than about 3 ppm.

In various embodiments, catalytically stabilizing the bio-oil mayinclude contacting the bio-oil to a stabilizing catalyst. Thestabilizing catalyst may include a metal dispersed on a solid support,e.g., a metal oxide, a zeolite, carbon, and the like, which may beacidic. For example, the metal may include one or more of: Ru, Rh, Re,Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The metal oxide may include one ormore of: titania, ceria, magnesium oxide, niobium oxide, alumina,amorphous silica alumina, zirconia, zinc oxide, niobic acid, tungsticacid, molybdic acid, carbon, and silica.

The method may include contacting the bio-oil to a diluting medium toform a diluted bio-oil. The method may include diluting the bio-oil inan organic solvent to form a diluted bio-oil. The organic solvent mayinclude a protic organic solvent, e.g., an alcohol. The organic solventmay include an aprotic organic solvent. The organic solvent may includea polar solvent. The organic solvent may include a polar protic solvent.The organic solvent may include a polar aprotic solvent. The organicsolvent may include a nonpolar solvent. The diluting medium may includean organic solvent including one or more of: a protic solvent, anaprotic solvent, a polar solvent, and a nonpolar solvent. The dilutingmedium may include an organic solvent including one or more of:methanol, ethanol, 2-propanol, n-butanol, sec-butanol, tert-butanol,pentanol, hexanol, methyl cyclohexanol, acetone, methyl ethyl ketone,butanone, ethyl acetate, tetrahydrofuran, methyl tert-butyl ether,diethyl ether, acetonitrile, dimethyl formamide, dimethylsulfoxide, andthe like. The method may include diluting the bio-oil in a petroleumfuel to form a diluted bio-oil. The petroleum fuel may include one ormore of: diesel, gasoline, kerosene, jet fuel, fuel oil, naptha,fractions thereof, combinations thereof, and the like. The method mayinclude diluting the bio-oil in a portion of the stabilized bio-oil toform the diluted bio-oil. The portion of the stabilized bio-oil mayinclude a light phase. The light phase may include water. The portion ofthe stabilized bio-oil may include a heavy phase. The heavy phase mayinclude the bio-oil. The portion of the stabilized bio-oil may includeone or more of: the light phase and the heavy phase. The method mayinclude diluting the bio-oil to form the diluted bio-oil in one or moreof: an organic solvent, a petroleum fuel, water, and a portion of thestabilized bio-oil.

The method may include diluting the bio-oil in a diluting medium to forma diluted bio-oil. Diluting the bio-oil in the diluting medium mayinclude diluting the bio-oil to a percentage by weight of the dilutingmedium of about one or more of: 5 to 50, 10 to 45, 15 to 40, 20 to 35,25 to 35, and 30.

The method may include contacting the bio-oil to a diluting medium toform a diluted bio-oil using a positive pressure differential in poundsper square inch compared to atmospheric pressure of at least about oneor more of: 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150,175, 200, 500, 1000, 1500, 1800, and 2000.

The method may include contacting the bio-oil to a diluting medium toform a diluted bio-oil and catalytically stabilizing the bio-oil.Catalytically stabilizing the bio-oil may include contacting the dilutedbio-oil to the stabilizing catalyst.

The method may include removing at least a portion of the dilutingmedium from the diluted bio-oil after catalytically stabilizing thediluted bio-oil. The diluting medium may include one or more of: theorganic solvent, the petroleum fuel, and the water. The removed dilutingmedium may be recycled.

In some embodiments, catalytically stabilizing the bio-oil may includecontacting the bio-oil to a stabilizing catalyst that includes azeolite. Further, the solid support may be a zeolite, e.g., an acidiczeolite. The zeolite may include one or more of: a Y zeolite, a Betazeolite, a ZSM-5 zeolite, a Mordenite zeolite, a Ferrierite zeolite, aAl-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22 zeolite, a SAPO-34zeolite, and a Chabazite zeolite.

In various embodiments, the stabilizing catalyst may include the metaldispersed on an acidic metal oxide, For example, the stabilizingcatalyst may include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni,Nb, and Os; dispersed on one or more of: titania, ceria, magnesiumoxide, niobium oxide, alumina, amorphous silica alumina, zirconia, zincoxide, niobic acid, tungstic acid, molybdic acid, carbon, and silica.For example, catalytically stabilizing the bio-oil may includecontacting the bio-oil to a stabilizing catalyst including Ru/TiO₂.

In some embodiments, the stabilizing catalyst may include the metaldispersed on an acidic zeolite. For example, the stabilizing catalystmay include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, andOs; dispersed on one or more of: a Y zeolite, a Beta zeolite, a ZSM-5zeolite, a Mordenite zeolite, a Ferrierite zeolite, a Al-MCM-41 zeolite,a MCM-48 zeolite, a MCM-22 zeolite, a SAPO-34 zeolite, and a Chabazitezeolite.

In several embodiments, catalytically stabilizing the bio-oil mayinclude contacting the bio-oil to a stabilizing catalyst at atemperature in ° C. of about one or more of: 40 to 300, 100 to 280, 120to 270, 130 to 250, 140 to 225, 150 to 200, 160 to 180, and 170.Catalytically stabilizing the bio-oil may include contacting the bio-oilto a stabilizing catalyst at a pressure in PSI of about one or more of:500 to 2500, 750 to 2250, 1000 to 2000, 1250 to 1750, 1400 to 1600, and1500. Catalytically stabilizing the bio-oil may include contacting thebio-oil to a stabilizing catalyst in the presence of hydrogen.Catalytically stabilizing the bio-oil may include providing asubstantial excess of hydrogen at a pressure in pounds per square inchgauge of one or more of: 100 to 2000, 500 to 1800, and 1000 to 1500.Catalytically stabilizing the bio-oil may include flowing the bio-oilpast a stabilizing catalyst at a liquid hourly space velocity (LHSV) ofbetween about 0.05 hr⁻¹ to 1 hr⁻¹. Catalytically stabilizing the bio-oilmay include contacting the bio-oil to a stabilizing catalyst for a TOSin hours of at least about one or more of: 200, 300, 400, 500, 600, 700,800, 900, 1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000,4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and 16,000.

In several embodiments, the method may include regenerating thestabilizing catalyst, for example, by rinsing the stabilizing catalystwith an organic solvent. The organic solvent may include a proticorganic solvent, e.g., an alcohol. The organic solvent may include oneor more of methanol, ethanol, 2-propanol, n-butanol, sec-butanol,tert-butanol, pentanol, hexanol, methyl cyclohexanol, acetone, methylethyl ketone, butanone, ethyl acetate, tetrahydrofuran, methyltert-butyl ether, acetonitrile, dimethyl formamide. The method mayinclude regenerating the stabilizing catalyst by contacting thestabilizing catalyst with hydrogen at a temperature in ° C. of about oneor more of: 250 to 550, 300 to 500, 325 to 475, 350 to 450, 375 to 425,and 400. For example, the hydrogen may chemically reduce carbonaccumulation on the stabilizing catalyst to produce gaseous methane.Such reducing may be desirable compared to oxidative methods of removingcarbon, because hydrogen reduction of carbon to methane may be lessexothermic than carbon oxidation in the presence of oxygen, leading toless heating and less thermal damage to the stabilizing catalyst, e.g.,by sintering.

In various embodiments, the stabilized bio-oil may be characterizedcompared to the bio-oil. For example, the stabilized bio-oil may becharacterized compared to the bio-oil by a decreased content ofaldehydes and free carboxylic acids. The stabilized bio-oil may becharacterized compared to the bio-oil by an increase in pH of at leastone or more of about: 0.25, 0.5, 0.75, 1, 1.25, and 1.5. The stabilizedbio-oil may be characterized compared to the bio-oil by a percentincrease in dry hydrogen:carbon ratio of one or more of about: 5, 10,15, 20, and 25. The stabilized bio-oil may be characterized compared tothe bio-oil by one or more of the characteristics recited in thisparagraph.

In some embodiments, the bio-oil may be characterized by one or more of:a density of about 1 to 1.2 grams per milliliter, a dry hydrogen:carbonratio of about 1.4:1, a dry oxygen weight percentage of about 20% to35%, and a water weight percentage of about 30% to 45%. The stabilizedbio-oil may be characterized by one or more of: a density of about 1 to1.1 grams per milliliter, a dry hydrogen:carbon ratio of about 1.2:1 to1.8:1, a dry oxygen weight percentage of about 20% to 35%, and a waterweight percentage of about 20% to 35%.

FIG. 4 is a block diagram illustrating an example system 400 for forminga hydrocarbon product from biomass. In various embodiments, system 400may include a pyrolysis reactor 402 configured to pyrolyze a biomassinput and provide a bio-oil output. System 400 may include an inlinefilter 404 operatively coupled to receive the bio-oil output. Inlinefilter 404 may be configured to remove at least a portion of particleshaving an effective diameter greater than about 10 micrometers from thebio-oil output to provide a coarse-filtered bio-oil output. System 400may include a fine filtration module 406 configured to receive thecoarse-filtered bio-oil output. Fine filtration module 406 may beconfigured to remove at least a portion of particles having an effectivediameter greater than about 5 micrometers to provide a fine-filteredbio-oil output. System 400 may include a bed 408 configured to receivethe fine-filtered bio-oil. Bed 408 may be configured to remove at leasta portion of inorganic species from the fine filtered bio-oil to producea reduced-inorganic bio-oil output. Bed 408 may be configured toconfigured to contain one or more of: an ion exchange resin, a zeolite,and activated carbon. The ion exchange resin may include any ionexchange resin described herein. The zeolite may include any zeolitedescribed herein. System 400 may include a first catalytic unit 410configured to contain a stabilizing catalyst effective to receive thereduced-inorganic bio-oil. First catalytic unit 410 may be configured tostabilize the reduced-inorganic bio-oil to produce a stabilized bio-oiloutput. System 400 may include a second catalytic unit 412 configured tocontain a hydrotreatment catalyst effective to receive the stabilizedbio-oil. Second catalytic unit 412 may be configured to hydrotreat thestabilized bio-oil to provide a hydrocarbon output. System 400 mayinclude a hydrogen source 414 operatively coupled to provide hydrogen toone or more of first catalytic unit 410 and second catalytic unit 412.

In some embodiments, pyrolysis reactor 402 may include a downflowpyrolysis reactor. Pyrolysis reactor 402 may be configured to heat to atemperature in ° C. of at least about one or more of: 400 to 600, 400 to550, and 450 to 500.

In several embodiments, system 400 may include a condenser module 416.Condenser module 416 may include a three-stage condenser. Condensermodule 416 may include an electrostatic precipitator. Condenser module416 may be operatively coupled between pyrolysis reactor 402 and inlinefilter 404 such that inline filter 404 is configured to receive thebio-oil output in condensed form from condenser module 416. Inlinefilter 404 may be directly coupled to pyrolysis reactor 402 such thatinline filter 404 may be configured to receive the bio-oil output invapor form from pyrolysis reactor 402. Inline filter 404 may include oneor more of: a bag filter element, a metal mesh filter element, and aceramic filter element. Inline filter 404 may be configured to remove atleast a portion of particles having a diameter in micrometers greaterthan one or more of about: 10, 9, 8, 7, 6, 5, 4, and 2.

In various embodiments, fine filtration module 406 may be a stand-aloneunit (not shown). Fine filtration module 406 may operatively coupleinline filter 404 and bed 408 such that fine filtration module 406 maybe configured for inline operation. Fine filtration module 406 may beconfigured to remove at least a portion of particles having a diameterin micrometers greater than one or more of about: 4, 3, 2.5, 2, 1.5, 1,0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, and 0.1. Fine filtration module406 may include one or more of: a bag filter element, a metal meshfilter element, and a ceramic filter element. Fine filtration module 406may be operatively coupled to a pressure source 406A configured tooperate fine filtration module 406 using a pressure differential inpounds per square inch of at least about one or more of: 5, 10, 15, 20,30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, and 200. Fine filtrationmodule 406 may be operatively coupled to a heat source 406B configuredto operate fine filtration module 406 at a temperature in ° C. of atleast about one or more of: 30, 40, 50, 60, 70, 80, 90, and 100.

In some embodiments, bed 408 may be configured in the form of afixed-bed column reactor or a slurry bed reactor. For example, thefixed-bed column reactor may be configured for continuous orintermittent flow operation. The slurry bed reactor may be configuredfor batch operation. Bed 408 may include the ion exchange resin. Bed 408may be operatively coupled to a pressure source 408A configured tooperate bed 408 at a pressure in pounds per square inch of at leastabout one or more of: gauge (PSIG) of about one or more of: 0 to 100, 10to 100, 10 to 75, 10 to 50, 10 to 25, and 10 to 20. Bed 408 may beoperatively coupled to a heat source 408B configured to operate bed 408at a temperature in ° C. of about one or more of: 25 to 100, 25 to 75,30 to 50, 35 to 45, and 40, for example, 40° C. Bed 408 may include asthe ion exchange resin one or more of: a poly(styrene sulfonic acid), apoly(styrene carboxylic acid), and apoly(2-acrylamido-2-methyl-1-propanesulfonic acid). For example, the ionexchange resin may include a poly(styrene sulfonic acid) characterizedby one or more of: a surface area of about 28 to 37 square meters pergram, a particle diameter of 0.60 to 0.850 millimeters, a particlediameter uniformity coefficient of less than about 1.6, a total porevolume of 0.15 to 0.25 milliliters per gram, an average pore diameter ofabout 200 to 280 angstroms, and an exchange capacity of at least about 5milliequivalents per gram.

In several embodiments, first catalytic unit 410 may include thestabilizing catalyst. The stabilizing catalyst may include a metaldispersed on a solid support, e.g., a metal oxide, a zeolite, carbon,and the like, which may be acidic. The metal may include one or more of:Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The metal oxide mayinclude one or more of: titania, ceria, magnesium oxide, niobium oxide,alumina, amorphous silica alumina, zirconia, zinc oxide, niobic acid,tungstic acid, molybdic acid, carbon, and silica.

In some embodiments, the stabilizing catalyst may include a zeolite,e.g., an acidic zeolite. Further, the solid support may be a zeolite,e.g., an acidic zeolite. The zeolite may include one or more of: a Yzeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, aFerrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.

In various embodiments, the stabilizing catalyst may include the metaldispersed on an acidic metal oxide, For example, the stabilizingcatalyst may include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni,Nb, and Os; dispersed on one or more of: titania, ceria, magnesiumoxide, niobium oxide, alumina, amorphous silica alumina, zirconia, zincoxide, niobic acid, tungstic acid, molybdic acid, carbon, and silica.For example, catalytically stabilizing the bio-oil may includecontacting the bio-oil to a stabilizing catalyst including Ru/TiO₂.

In some embodiments, the stabilizing catalyst may include the metaldispersed on an acidic zeolite. For example, the stabilizing catalystmay include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, andOs; dispersed on one or more of: a Y zeolite, a Beta zeolite, a ZSM-5zeolite, a Mordenite zeolite, a Ferrierite zeolite, a Al-MCM-41 zeolite,a MCM-48 zeolite, a MCM-22 zeolite, a SAPO-34 zeolite, and a Chabazitezeolite.

In various embodiments, first catalytic unit 410 may be operativelycoupled to a pressure source 410A configured to operate first catalyticunit 410 at a pressure in PSI of about one or more of: 500 to 2500, 750to 2250, 1000 to 2000, 1250 to 1750, 1400 to 1600, and 1500. Firstcatalytic unit 410 may be operatively coupled to a heat source 410Bconfigured to operate first catalytic unit 410 at a temperature in ° C.of about one or more of: 40 to 300, 100 to 280, 120 to 270, 130 to 250,140 to 225, 150 to 200, 160 to 180, 170, 250 to 550, 300 to 500, 325 to475, 350 to 450, 375 to 425, and 400. First catalytic unit 410 may beconfigured to operate at a liquid hourly space velocity (LHSV) ofbetween about 0.05 hr⁻¹ to 1 hr⁻¹. First catalytic unit 410 may beconfigured to operate for a TOS in hours of at least about one or moreof: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1,100, 1,200, 1,300,1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000,12,000, and 16,000. First catalytic unit 410 may be operatively coupledto an organic solvent source 410C.

In some embodiments, system 400 may include a heat exchanger 418operatively coupled between first catalytic unit 410 and secondcatalytic unit 412. Heat exchanger 418 may be configured to actively orpassively limit heating of first catalytic unit 410 by heat from secondcatalytic unit 412.

In several embodiments, second catalytic unit 412 may include thehydrotreatment catalyst. The hydrotreatment catalyst may be an activemetal catalyst or a sulfided catalyst. For example, the active metalcatalyst may include a metal dispersed on a solid support, e.g., a metaloxide, a zeolite, carbon, and the like, each of which may be acidic. Forexample, the metal may include one or more of: Ru, Rh, Re, Pt, Pd, Ir,Au, Fe, Ni, Nb, and Os. The metal oxide may include one or more of:titania, ceria, magnesium oxide, niobium oxide, alumina, amorphoussilica alumina, zirconia, zinc oxide, niobic acid, tungstic acid,molybdic acid, carbon, and silica. The hydrotreatment catalyst mayinclude a zeolite. Further, the solid support may be a zeolite, e.g., anacidic zeolite. The zeolite may include one or more of: a Y zeolite, aBeta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a Ferrieritezeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22 zeolite, aSAPO-34 zeolite, and a Chabazite zeolite.

In various embodiments, the hydrotreatment catalyst may include themetal dispersed on an acidic metal oxide, For example, thehydrotreatment catalyst may include a metal including one or more of:Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The metal may bedispersed on a solid support comprising one or more of: titania, ceria,magnesium oxide, niobium oxide, alumina, amorphous silica alumina,zirconia, zinc oxide, niobic acid, tungstic acid, molybdic acid, carbon,silica, a Y zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenitezeolite, a Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, aMCM-22 zeolite, a SAPO-34 zeolite, a Chabazite zeolite, and carbon. Forexample, the active metal catalyst may include one or more of Ru/TiO₂,Ru/TiO₂—ZSM5 Pd/C, Pd/SiO₂—Al₂O₃, Pd/Nb/Al₂O₃, Pd/Nb/TiO₂—SiO₂,Pt/ZrO₂—Al₂O₃, and Pd/Mg/Al₂O₃.

Further, for example, the hydrotreatment catalyst may include a sulfidedcatalyst, e.g., including one or more of: Ni, Nb, Mo, Co, and W. Forexample, the sulfided catalyst may include one or more of sulfided: Ni,Nb, Mo, Co, W, NiMo, and CoMo.

In several embodiments, second catalytic unit 412 may include a pressuresource 412A configured to pressurize second catalytic unit 412 to apressure in PSI of about one or more of: 500 to 2500, 750 to 2250, 1000to 2000, 1250 to 1750, 1400 to 1600, and 1500. Second catalytic unit 412may include a heat source 412B configured to heat second catalytic unit412 to a temperature in ° C. of about one or more of: 200 to 420, 220 to400, 240 to 380, 260 to 360, 280 to 340, 300 to 320, and 310. Secondcatalytic unit 412 may be configured to operate at a liquid hourly spacevelocity (LHSV) of between about 0.05 hr⁻¹ to 1 hr⁻¹. Second catalyticunit 412 may be configured to operate for a TOS in hours of at leastabout one or more of: 200, 300, 400, 500, 600, 700, 800, 900, 1000,1,100, 1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000,6,000, 7,000, 8,000, 12,000, and 16,000.

In various embodiments, system 400 may include an inert gas source 420operatively coupled to provide an inert atmosphere to at least a portionof system 400. Inert gas source 410 may be configured to provide one ormore of: nitrogen, carbon dioxide, and a non-condensable gas product ofbiomass pyrolysis. Inert gas source 410 may be coincident with, the sameas, or operatively coupled to one or more of pressure sources 406A,408A, 410A, and 412A. Hydrogen source 414 may be coincident with, thesame as, or operatively coupled to one or more of pressure sources 406A,408A, 410A, and 412A. Two or more of pressure sources 406A, 408A, 410A,and 412A may be coincident, the same as each other, or operativelycoupled to each other. Two or more of heat sources 406B, 408B, 410B, and412B may be coincident, the same as each other, or operatively coupledto each other.

In some embodiments, pyrolysis reactor 402, inline filter 404, finefiltration module 406, bed 408, first catalytic unit 410, and secondcatalytic unit 412 may be operatively coupled to provide a continuousprocess for converting the biomass input to the hydrocarbon output.

In several embodiments, system 400 may be configured to operate for aTOS in hours of at least about one or more of: 200, 300, 400, 500, 600,700, 800, 900, 1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750, 2,000,3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and 16,000.

In various embodiments, a stabilized bio-oil is provided, preparedaccording to any of the methods described herein or prepared using anyof the systems described herein. In various embodiments, a hydrocarbonproduct derived from bio-oil is provided, prepared according to any ofthe methods described herein or prepared using any of the systemsdescribed herein.

In some embodiments, a stabilized bio-oil is provided. The stabilizedbio oil may be characterized by one or more of: a total acid number(TAN) value less than 100 mg KOH/g; a water content of at least about 17wt. %; a hydrogen to carbon ratio greater than 1.4:1; and an averagepercentage of aldehyde and ketone groups of less than about 5%.

In several embodiments, a hydrocarbon product derived from bio-oil isprovided. The hydrocarbon product may be characterized by one or more ofthe following. The hydrocarbon product may be characterized by one ormore percentages by weight of: about 24% paraffin, about 5.6% aromatics,about 8.6% naphthalenes, about 59% nC₅-C₆ alkanes, and about 2.4%olefins. The hydrocarbon product may be characterized by one or more of:a density in grams/mL of 0.78-0.86; a total sulfur weight percent ofless than 0.08%; a pour point in ° C. of less than about 20; a viscosityin cPs of less than 2; a hydrogen:carbon atomic ratio of about 1.5:1 toabout 2.2:1; and an energy value in mega Joules per kilogram of about 40to 45. The hydrocarbon product may be characterized by one or more of: adensity of about 0.8 to about 0.86 grams per milliliter, ahydrogen:carbon ratio of about 1.5:1 to about 2.2:1, a dry oxygen weightpercentage of about 0% to about 5%, and a water weight percentage ofabout 0% to about 5%.

EXAMPLES Example 1 Preparation of Synthetic Bio-Oils with and withoutInorganic Species

Four synthetic bio-oil compositions were prepared to determine theeffects inorganic species had in deactivating the hydrotreatmentcatalyst. The synthetic bio-oils included a mixture of chemicals withfunctional groups similar to those found in pyrolytic bio-oil. Thesynthetic bio-oil compositions included carboxylic acids, aldehydes,phenols, polyols, and water, effective to give the synthetic bio-oil asimilar oxygen concentration (28% wt) as pyrolytic bio-oil. Inorganicspecies were provided in synthetic bio-oil compositions that includedmetal concentrations comparable to that of pyrolytic bio-oil. The tablein FIG. 5 reports species concentrations determined from inductivelycoupled plasma (ICP) atomic analyses of pyrolytic bio-oil and syntheticbio-oil.

A first synthetic bio-oil composition without inorganic species wasprepared by mixing acetic acid (6.8% by volume), hydroquinone (9.1% byvolume), D-glucose (7.8% by volume), 4-hydroxybenzoic acid (8.0% byvolume), methanol (50.7% by volume) and water (17.6% by volume). Themethanol was added to the mixture in order to solubilize hydroquinoneand 4-hydroxybenzoic acid.

A second synthetic bio-oil composition with inorganic species wasprepared by mixing acetic acid (6.8% by volume), hydroquinone (9.1% byvolume), D-glucose (7.8% by volume), 4-hydroxybenzoic acid (8.0% byvolume), methanol (50.7% by volume), water (17.6% by volume), calcium(101 ppm) in the form of calcium hydroxide, zinc (52 ppm) in the form ofzinc acetate, sodium (49 ppm) in the form of sodium hydroxide, potassium(49 ppm) in the form of potassium carbonate, magnesium (99 ppm) in theform of magnesium carbonate, iron (148 ppm) in the form of iron acetate,aluminum (287 ppm) in the form of aluminum lactate, phosphorus (50 ppm)in the form of phosphorus pentoxide, and sulfur (50 ppm).

A third synthetic bio-oil composition with heteroatom-containing specieswas prepared by mixing acetic acid (6.8% by volume), hydroquinone (9.1%by volume), D-glucose (7.8% by volume), 4-hydroxybenzoic acid (8.0% byvolume), methanol (50.7% by volume), water (17.6% by volume), calcium(101 ppm) in the form of calcium hydroxide, zinc (52 ppm) in the form ofzinc acetate, sodium (49 ppm) in the form of sodium hydroxide, potassium(49 ppm) in the form of potassium carbonate, magnesium (99 ppm) in theform of magnesium carbonate, iron (148 ppm) in the form of iron acetate,aluminum (287 ppm) in the form of aluminum lactate, and phosphorus (50ppm) in the form of phosphorus pentoxide. The third synthetic bio-oilcomposition with inorganic species did not include a sulfur additive. Afourth synthetic bio-oil composition with inorganic species was preparedby mixing acetic acid (6.8% by volume), hydroquinone (9.1% by volume),D-glucose (7.8% by volume), 4-hydroxybenzoic acid (8.0% by volume),methanol (50.7% by volume), water (17.6% by volume), and iron (148 ppm)in the form of iron acetate.

Example 2 Hydrotreatment of Synthetic Bio-Oil without Inorganic Species

The first synthetic bio-oil without inorganic species was subjected tohydrotreatment under various conditions. The efficiency of the catalystsystem was determined by analyzing the products obtained from thehydrotreatment process:

1) The catalyst was considered to be active if a biphasic productresulted with an organic phase with a density of less than 0.8 g/cm³ anda water content of less than 5%. An aqueous phase with a density ofapproximately 1 g/cm³ and a water content greater than 90% wasdesirable. The hydro-deoxygenation reaction scheme is illustrated below:

Catalyst deactivation was indicated by an increase in the density of theorganic phase corresponding to an increase in water content in theorganic phase. An increase in density and water content in the organicphase may result from remaining bio-oil hydroxyls that may effectivelyhydrogen bond with water, thus drawing the water into the organic phase.Remaining bio-oil hydroxyls may be indicative of an inefficient ordeactivated catalyst.

2) Measurement of non-condensable gases (R-H at higher temperatures;C₁-C₆ hydrocarbons) released from the reaction mixture indicatedcatalyst activity since the detection of such gases suggested thathydro-deoxygenation was successful. Methanol used to solubilize thesynthetic bio-oil composition was converted to methane underhydro-deoxygenation conditions. Thus, assessment of the catalystactivity was made by detection of the gaseous C₂-C₆ hydrocarbons by gaschromatography (GC) analysis.

The first synthetic bio-oil without inorganic species was subjected tohydrotreatment under the conditions illustrated in FIGS. 6A-6C. Thesynthetic bio-oil was subjected to Zone I at 150° C. and passed over aRu/TiO₂ catalyst at a liquid hourly space velocity (LHSV) of 0.2 h⁻¹ inthe presence of H₂ at a 400 mL/min flow rate. The reaction mixture fromZone I was subsequently subjected to Zone II at 280° C. and passed overa Ru/TiO₂—ZSM5 catalyst at a LHSV of 0.2 h⁻¹ in the presence of H₂ at a400 mL/min flow rate (entry 1, FIG. 6C). Samples were analyzed every 4-8h for a duration of 0-40 h Time on Stream (TOS) (see graph in FIG. 6D,and sections A and B in FIG. 6D for parameters). The majority of thesynthetic bio-oil was released as gaseous hydrocarbons. The condensedliquid phase obtained was mostly aqueous.

At 40 h TOS to 48 h TOS, the H₂ flow rate had been increased from 400mL/min to 600 mL/min, and the LHSV was increased from 0.2 h⁻¹ to 0.4h⁻¹. The Zone I temperature was maintained at 150° C. and the Zone IItemperature was maintained at 280° C. (entry 2, FIG. 6C). Samples wereanalyzed every 4-8 h by GC (see graph in FIG. 6D, and sections B, C, andD in FIG. 6D). Increasing the H₂ flow and the LHSV did not lead to abiphasic mixture.

At 48 h TOS to 60 TOS, the temperature of Zone II was decreased from280° C. to 150° C. The Zone I temperature was maintained at 150° C., theH₂ flow rate was maintained at 600 mL/min, and the LHSV was maintainedat 0.4 h⁻¹ (entry 3, FIG. 6C). Samples were analyzed every 4-8 h (seegraph in FIG. 6D, and sections C, D, E, and F in FIG. 6D). Decreasingthe temperature in Zone II, the hydro-deoxygenation zone, led to poorcatalytic activity. Although a biphasic mixture was obtained, theorganic phase contained approximately 30% water.

At 60 h TOS to 170 h TOS, the temperature of Zone I was increased from150° C. to 200° C. and the temperature of Zone II was increased from150° C. to 200° C. The H₂ flow rate was maintained at 600 mL/min and theLHSV was maintained at 0.4 h⁻¹ (entry 4, FIG. 6C, see sections C, D, andG in FIG. 6D). A biphasic mixture of hydrocarbons and water wasobtained. The organic phase had less than 1% water content and theaqueous phase was more than 90% water.

Example 3 Hydrotreatment of Synthetic Bio-Oils with and withoutInorganic Species: Analysis of Organic Phase Density

Based on the results of EXAMPLE 2, operative conditions of Zone I andZone II at 200° C. and a LHSV of 0.2 h⁻¹ were used for studying thehydrotreatment of synthetic bio-oils with and without inorganic species.FIG. 6E illustrates the density of the organic phase obtained relativeto time on system (TOS) for the first, second, third, and fourthsynthetic bio-oil compositions described in EXAMPLE 1. The density ofthe organic phase did not increase over time for the first syntheticbio-oil composition without inorganic species. The addition of iron inthe fourth synthetic bio-oil did not adversely affect the density of theorganic phase product until after 24 h, which indicated that thecatalyst had begun to lose activity. The addition of other heteroatoms,such as those of the second and third synthetic bio-oils described inEXAMPLE 1, corresponded to a rapid increase in the density of theorganic phase product. From this experiment, it was concluded thatinorganic species deactivate the catalyst.

Example 4 Hydrotreatment of Synthetic Bio-Oils with and withoutInorganic Species: Analysis of Organic Phase Water Content

Based on the results of EXAMPLE 2, operative conditions of Zone I andZone II at 200° C. and a LHSV of 0.2 h⁻¹ where used for studying thehydrotreatment of synthetic bio-oils with and without inorganic species.FIG. 6F illustrates the water content of the organic phase obtainedrelative to the TOS for the first, second, third, and fourth syntheticbio-oil compositions described in EXAMPLE 1. The water content of theorganic phase remained low throughout the TOS, which indicated that thecatalytic reduction was sustainable. Had the catalyst become deactivatedover time, it was expected that the unreacted hydroxyl-containingmoieties in the organic phase would effectively increase the organicphase water content. Complimentary to the results in EXAMPLE 3, theaddition of iron as in the fourth synthetic bio-oil did not adverselyaffect the water content of the organic phase product until after 24 h,which indicated that the catalyst had begun to lose activity. Theaddition of other heteroatoms, such as those provided in the second andthird synthetic bio-oils described in EXAMPLE 1, corresponded to a rapidincrease in the water content of the organic phase product. Inconjunction with EXAMPLE 3, this experiment suggests that inorganicspecies deactivate the catalyst.

Example 5 Hydrotreatment of Synthetic Bio-Oils with and withoutInorganic Species: Analysis of Gaseous C₂-C₆ Hydrocarbons Produced

Based on the results of EXAMPLE 2, operative conditions of Zone I andZone II at 200° C. and a LHSV of 0.2 h⁻¹ were used for studying thehydrotreatment of synthetic bio-oils with and without inorganic species.FIG. 6G illustrates the C₂-C₆ hydrocarbon concentration in thenon-condensable gas relative to the TOS in the hydrotreatment processfor the first, second, third, and fourth synthetic bio-oil compositionsdescribed in EXAMPLE 1. The concentration of C₂-C₆ hydrocarbons remainedconstant throughout TOS for the first synthetic bio-oil withoutinorganic species, which indicated that the catalytic reduction wassustainable. Complimentary to the results in EXAMPLES 3 and 4, theaddition of iron as in the fourth synthetic bio-oil did not adverselyaffect the concentration of C₂-C₆ hydrocarbons released until after 24h, which indicated that the catalyst had begun to lose activity. Theaddition of other heteroatoms, such as those provided in the second andthird synthetic bio-oils described in EXAMPLE 1, corresponded to a rapiddecrease in the concentration of C₂-C₆ hydrocarbons released. Inconjunction with EXAMPLES 3 and 4, this experiment suggests thatinorganic species deactivate the catalyst.

Example 6 Hydrotreatment of Pyrolysis Bio-Oil

The results described in EXAMPLES 2-5 suggested that inorganic speciesin the bio-oil deactivated the hydrotreatment catalysts. It washypothesized that pyrolytic bio-oil would be a better feedstock forhydrotreatment in that the fluid-cracking catalyst (FCC) used in thevapor phase catalytic reactor may have removed some of the inorganicspecies during the pyrolysis process. The organic phase obtained fromthe pyrolysis process was blended with methanol (10% wt) to improve thehomogeneity of the bio-oil feedstock. The pyrolysis bio-oil compositionwas subjected to hydrotreatment for 50 h TOS with fresh catalyst, asillustrated in FIG. 7. Samples were analyzed every 8 h. After 50 h, thedensity of the organic phase obtained had increased from 0.7 g/cm⁻³ to0.9 g/cm⁻³, which indicated degradation of product quality and suggesteddeactivation of the catalyst. The catalyst was regenerated by rinsingwith methanol at room temperature, and reducing with H₂ at 400° C.Hydrotreatment was resumed and revealed an increase in deactivation rate(the organic phase densities increased at a faster rate). The catalystwas regenerated two additional times, and each subsequent hydrotreatmentprocess produced a decrease in product quality at increasingly fasterrates. The increase in deactivation rates from cycle to cycle suggestednon-reversible catalyst deactivation. The C₂-C₆ hydrocarbonnon-condensable gases were also monitored during the experiments. Thedata from gaseous C₂-C₆ hydrocarbon detection correlated with the dataobtained in the organic phase analyses.

The pyrolysis bio-oil used in EXAMPLE 6 was obtained from a pyrolysisprocess using a spent FCC catalyst. Bio-oil obtained from the use offresh FCC catalyst may effectively increase the removal of inorganicspecies prior to hydrotreatment. However, the focus in removinginorganic species prior to hydrotreatment turned to other means asdescribed below.

Example 7 Production of Intermediate Bio-Oil

Bio-oil was produced using a continuous feed pyrolysis system having a 1ton per day capacity. A pine saw dust with a particle size between 2 to5 mm was continuously fed into the pyrolysis system as a feedstock. Thepyrolysis temperature was between 450° C. and 500° C. The yield wasapproximately 65-70% bio-oil by weight based on initial biomass weightwith a water content of 35-40%. The bio-oil was condensed and filteredvia a two filter system as follows. A 10 micrometer filter was coupledto the pyrolysis output just after condensation to provide acoarse-filtered bio-oil. The coarse-filtered bio-oil was then directedto an ex-situ filter module that included a 0.8 micron. Using pressureup to 80 psi, the coarse-filtered bio-oil was driven through the 0.8micron to provide a fine-filtered bio-oil. This fine-filtered bio-oilwas collected and reserved for further EXAMPLES as described below.

Example 8 Deactivation of Stabilization Catalyst is Associated withInorganic Contaminants

It is known that stabilization catalysts are readily deactivated incontact with bio-oil. To determine the root cause of catalystdeactivation, fresh and spent stabilization catalysts were characterizedafter 500 h TOS.

The fresh (reduced at 400° C.), spent (500 h TOS and washed withmethanol) and regenerated (spent, washed with methanol and reduced)catalysts were analyzed by thermos-gravimetric analysis in the presenceof air from 120° C. (held for 30 min) to 700° C. (held for 30 min) at arate of 10° C./min. The weight loss for the spent catalyst wasapproximately 24%. Reduction of the catalyst at 400° C., 450° C., and500° C. successively removed 90%, 93% and 95% of material. This removalwas attributed to the oxidation of carbon on the catalyst to CO₂. Theremaining carbon (<10%) was thought to be bonded strongly to the highactive metal sites located in the micro pores. These active sites arethought to be difficult access, for example, due to diffusionlimitations, which may tend to prevent such sites from activelycontributing to catalysis at steady state. As a consequence, theregeneration of the catalyst was judged to be efficient and the cokeformation was not judged to be the main cause of catalyst deactivation.FIG. 8 summarizes the results of the thermogravimetric experiments.

FIGS. 9A and 9B are transmission electron microscope (TEM) photosshowing that the fresh and spent catalysts, respectively, had similarmetal particle sizes (2 to 8 nanometers) and metal dispersions. However,hydrogen adsorption data at room temperature indicated that the freshreduced catalyst had a metal dispersion of 12% and the regenerated spentcatalyst had a metal dispersion of less than 1%. This data indicatesthat the catalyst deactivation is not due to a loss of surface area dueto sintering.

FIG. 10 is a graph of ICP analysis of fresh and spent (post 500 h TOS)catalysts showing that deposition of inorganic contaminants such as Ca,Fe and S are associated with deactivated catalyst. The increase incertain inorganic metal contaminants not present in the bio-oil feed,such as the 1,500 ppm of Fe, may indicated that such species areleaching out of the steel of the hydrotreatment reactor.

By contrast, the small amounts of sulfur in the feed (8.92 ppm) comparedto the 1,800 ppm of sulfur on the catalyst after 500 h TOS was judged tooccur by accumulation of sulfur from the bio-oil feed on the catalyst.

In view of these results, EXAMPLE 9 was devised to remove inorganiccontaminants from the bio-oil prior to Zone I stabilization in order toreduce catalyst deactivation.

Example 9 Ion Exchange Media Removes Inorganic Species from Bio-Oil

EXAMPLE 8 corresponds to EXAMPLES 2-5 in describing inorganic speciespoisoning as the most probable cause of permanent deactivation ofhydrotreatment catalysts, with the poisoning being associated withinorganic salts and covalent sulfur containing compounds. Consequently,a variety of media were tested to remove the inorganic species andcovalent sulfur containing compounds from the bio-oil.

Preliminary tests showed that a polystyrene sulfonic acid ion exchangeresin (AMBERLYST™ 36, Dow Chemical Company, Midland, Mich.) effectivelyremoved many inorganic species. Samples of unfiltered, coarse-filtered,and fine-filtered bio-oil from both batch and flow reactors werecontacted to the polystyrene sulfonic acid ion exchange resin in aslurry reactor at about 40° C. for about 1 h. FIG. 11 reports theconcentration in parts per million of various inorganic species measuredvia inductively coupled plasma (ICP) atomic analysis for thefine-filtered bio-oil of EXAMPLE 7 before and after contact with thepolystyrene sulfonic acid ion exchange resin under various conditions.

A fixed bed flow reactor was prepared by loading the polystyrenesulfonic acid ion exchange resin into a column. A slurry bed batchreactor was prepared by loading the polystyrene sulfonic acid ionexchange resin into a 2 L three-necked flask equipped with a stirrer anda thermocouple. Both reactors were supplied with the fine-filteredbio-oil of EXAMPLE 7 under nitrogen and at 40° C.

FIG. 11 shows that the content of inorganic elements such as Al, Ca, Fe,K, Mg, Na, Si and S could be decreased, in many cases below 3.0 ppm,which suggested a successful removal of these inorganics from bio-oil.The fixed bed flow reactor worked well to remove inorganic species fromthe fine-filtered bio-oil to produce a reduced-inorganic bio-oil asshown for trial #1 in FIG. 11. However, with the benchtop equipmentavailable, the fixed bed flow reactor operated at an undesirably lowspace velocity. The slurry bed batch reactor required far less time toremove the inorganic contaminants. Accordingly, the slurry bed batchreactor was selected for use in further tests to produce thereduced-inorganic bio-oil.

In trial #2, operation of the slurry bed batch reactor on afine-filtered bio-oil with a relatively higher initial amounts of mostinorganic species was able to remove most species to a concentrationbelow about 6 ppm. In trial #3, operation of the slurry bed batchreactor on a fine-filtered bio-oil with a somewhat lower overall amountsof inorganic species was able to remove most species to a concentrationbelow about 3 ppm. The amount of K in trial #3 was removed to below 6ppm, which was still judged to be effective.

The minimal amount of sulfur-containing species removed in trial #3compared to other inorganic atoms was thought to indicate that mostsulfur-containing species contained sulfur covalently bonded in organiccompounds, with a lesser amount of sulfur present in the form of ionicspecies. By contrast, the effective removal of inorganic elements suchas Al, Ca, Fe, K, Mg, Na, and Si was thought to indicate the presence ofthese elements in ionic species which were readily adsorbed on the ionexchange resin. Six liters of cleaned, reduced-inorganic bio-oilproduced according to this EXAMPLE was collected and retained for use insubsequent EXAMPLES including stabilization and hydrogenation/cracking.

It was thought that if the sulfur was bound covalently, then it couldpotentially remain bound to the carbon under subsequent mildstabilization conditions, which could avoid sulfur poisoning of thestabilization catalyst in Zone I (EXAMPLE 10). It was further thoughtthat such stabilized, but sulfur-containing bio-oil would still be ansuitable substrate if a sulfided catalyst was used for subsequenthydrogenation and cracking in Zone II (EXAMPLE 11).

The fine-filtered bio-oil (before ion exchange treatment) and thereduced-inorganic bio-oil (after ion exchange treatment) were alsoexamined by ¹H NMR. FIGS. 18A and 18B illustrate ¹H NMR (proton nuclearmagnetic resonance) spectroscopy data of the fine-filtered bio-oil andthe reduced-inorganic bio-oil. FIG. 18A shows ¹H NMR overlay spectrafrom about 6 ppm to 13 ppm, wherein the bottom spectrum is the spectrumobtained from the fine-filtered bio-oil and the top spectrum is thespectrum obtained from the reduced-inorganic bio-oil. FIG. 18B shows ¹HNMR overlay spectra from 0 ppm to about 6 ppm, wherein the bottomspectrum is was obtained from the fine-filtered bio-oil and the topspectrum was obtained from the reduced-inorganic bio-oil. No changeswere observed in the functional groups associated with the bio-oil inthe ¹H NMR spectra. Thus, the ion exchange resin treatment at 40° C.reduced inorganic contaminants as shown in FIG. 10 without significantchemical modifications to the bio-oil.

Example 10 Use of Reduced-Inorganic Bio-Oil in Production of StabilizedBio-Oil (Zone I) Leads to 1,000 Hour TOS with Improved Catalyst Life andReduced Corrosion

Bio-oil hydrotreatment has been performed in a dual zone reactor, withstabilization in Zone I at about 150 to 300° C. and hydrogenation andcracking in Zone II at a higher temperature, e.g., 300 to 400° C.Previous experiments have shown that in a small-scale dual zone reactor,significant axial heat transfer takes place from the higher temperatureZone II to the lower temperature Zone I. This tends to cause undesirablyhigh temperatures in Zone I and poor temperature control, which can leadto accelerated coking and catalyst deactivation. Also, operation of acontinuous dual zone reactor does not readily permit sampling andanalysis of the bio-oil between Zones I and II, which is desirable inthese initial experiments. In addition, at the flow rates used insmall-scale test reactors, sulfur from Zone II may contaminate thecatalyst in Zone I. Accordingly, in these initial experiments, bio-oilstabilization in Zone I and hydrogenation/cracking in Zone II wereconducted separately. Separation of Zone I and Zone II in these initialexperiments allowed provided desired control of the operatingconditions. Production scale operations may operate Zone I and Zone IIdirectly in series while reducing thermal and sulfur backflow by usingone or more of higher flow rates, baffles, separation between zones,heat exchangers or insulated conduits between zones, and the like.Moreover, at production scale, sampling and analysis may not be neededbetween Zone I and Zone II.

The objective of the Zone I stabilization/hydrotreatment was to reducealdehydes and acids and to partially hydrogenate the bio-oil. Prior tohydrotreatment, the resin-treated bio-oil (38 wt % water; 1.1 g/cm³;pH=2) was diluted with methanol (30 wt %) to achieve a homogeneousbio-oil composition (24 wt % water; 0.99 g/cm³; pH=2.46) in order toprevent stratification in the delivery syringe pump, thus providing auniform feed to the reactor. Zone I stabilization/hydrotreatment wasconducted at high pressure in the presence of hydrogen. Hydrotreatmentwas conducted in three cycles using the same catalyst, Ru/TiO₂. Thecatalyst was regenerated twice during the three test cycles. The totalTOS achieved was 1,000 h at a LHSV of 0.2 h⁻¹. More than 3.5 liters ofbio-oil produced was processed. The Zone I stabilization/hydrotreatmentwas conducted in three cycles. After each cycle, the reactor wascarefully disassembled and a sample of catalyst was collected. Thecatalyst loading and flow rate for cycle 1 are presented in FIG. 12.

In cycle 1, the catalyst was subjected to reducing conditions in-situ at300° C. with hydrogen. The run started at 170° C. with a LHSV of 0.2 h⁻¹based on bio-oil. After 516 h TOS, an increase in differential pressureacross the catalyst bed related to carbon deposition on the catalyst wasnoted. The system was shut down and the catalyst was carefully removed.The spent catalyst was washed carefully with methanol to remove softcarbon, dried at 60° C., and loaded in the reactor to perform cycle 2.

In cycle 2, the catalyst as washed with methanol in cycle 1 wassubjected to reducing conditions in-situ at 400° C. with hydrogen toremove additional remaining carbon. Some of the catalyst was lost due towashing and repacking the catalyst. The flow of bio-oil was adjusted toreflect the loss of catalyst. The reaction was then resumed at 170° C.with a LHSV of 0.2 hr⁻¹. After 440 h TOS (cycle 2), the reactor startedplugging, at which point the reactor was shut down and the catalyst wascarefully removed. The spent catalyst was washed carefully with methanolto remove soft carbon, dried at 60° C., and loaded in the reactor toperform cycle 2.

In cycle 3, the catalyst as washed with methanol in cycle 2 wassubjected to reducing conditions in-situ at 400° C. with hydrogen toremove additional remaining carbon. Some of the catalyst was lost due towashing and repacking the catalyst. The flow of bio-oil was adjusted toreflect the loss of catalyst. The flow of bio-oil was adjusted toreflect these changes. The reaction was resumed at 170° C. and a LHSV of0.2 hr⁻¹. After 260 h TOS, the reaction was stopped as planned.

In some runs, the reduced-inorganic bio-oil of EXAMPLE 9 was dilutedwith methanol to improve homogeneity of the bio-oil and improve loadinginto the stabilization reactor with the available vertically-orientedbenchtop syringe pumps. The run described in FIG. 12, with a LHSV of 0.2hr⁻¹, was conducted in the absence of methanol.

In each cycle, the liquid yield (stabilized bio-oilproduct/reduced-inorganic bio-oil feed) was approximately 100%. Twophases were obtained during all cycles, a light phase (95% wt) with adensity of approximately 0.97 g/cm³ and a heavy phase (5% wt) with adensity of 1.07 (g/cm³). It was easier to discern two phases in thestabilized bio-oil during the first 400 h TOS. After 400 h TOS, thestabilized bio-oil had the appearance of a single phase. Since the yieldof the heavy phase was only about 5%, no measurement was made on theheavy phase after 400 h TOS. FIG. 13 graphs liquid and dry yield ratiosof (stabilized bio-oil product/cleaned bio-oil feed). Dry yield is thetotal yield excluding water.

FIG. 14 is a graph of the pH of the stabilized bio-oil product versusTOS. The pH of the liquid product increased from 2.4 (in thereduced-inorganic bio-oil feed) to 3.7 after treatment in Zone I.

FIG. 15 is a graph of water content in the liquid phase as determined bythe Karl Fisher method. Water content increased slightly in the lightphase to approximately 35% after cycle 1 relative to the water contentof the reduced-inorganic bio-oil feed (approximately 25%). Withoutwishing to be bound by theory, it is believed that this can be explainedby esterification reactions and interactions with aldehydes with otherfunctional groups such as acids, ketones and olefins as well asetherification reactions which may occur during Zone I stabilization.

The reduced-inorganic bio-oil (before Zone I) and the stabilized bio-oil(after Zone I) were also examined by ¹H NMR. FIGS. 19A and 19Billustrate ¹H NMR spectroscopy data of the reduced-inorganic bio-oil andthe stabilized bio-oil from 0-324 h TOS. FIG. 19A shows ¹H NMR overlayspectra from about 6 ppm to 13 ppm. The spectrum at TOS=0 h was obtainedfrom the reduced-inorganic bio-oil. The overlay spectra at TOS=55-60 h,106-112 h, 242-252 h, and 312-324 h were obtained from the stabilizedbio-oil at the corresponding TOS. FIG. 19B shows ¹H NMR overlay spectrafrom 0 ppm to about 6 ppm. The spectrum at TOS=0 h was obtained from thereduced-inorganic bio-oil. The overlay spectra at TOS=55-60 h, 106-112h, 242-252 h, and 312-324 h were obtained from the stabilized bio-oil atthe corresponding TOS.

FIGS. 20A and 20B illustrate data of the stabilized bio-oil from 466-478h TOS with respect to the reduced inorganic bio-oil at TOS=0 h. FIG. 20Ashows ¹H NMR overlay spectra from about 6 ppm to 13 ppm. The spectrum atTOS=0 h was obtained from the reduced-inorganic bio-oil. The overlayspectra at TOS=466-478 h, 502-514 h, 676-700 h, 773-797 h, 820-844 h,916-940 h, and 964-1010 h were obtained from the stabilized bio-oil atthe corresponding TOS. FIG. 20B shows ¹H NMR overlay spectra from 0 ppmto about 6 ppm. The spectrum at TOS=0 h was obtained from thereduced-inorganic bio-oil. The overlay spectra at TOS=466-478 h, 502-514h, 676-700 h, 773-797 h, 820-844 h, 916-940 h, and 964-1010 h wereobtained from the stabilized bio-oil at the corresponding TOS. The ¹HNMR spectra indicated that Zone I treatment caused led to reduction ofsignificant amounts of aldehyde and acid functional groups, partialhydrogenation of aromatics and olefins, and the appearance of newaliphatic compounds. These results indicate that esterification,etherification, and partial hydrogenation reactions were taking placeduring the Zone I stabilization/hydrotreatment. These reactions weremore pronounced in the first 500 h and then decreased as TOS progressed.The disappearance in carboxylic acid resonances suggested thatesterification reactions had occurred during Zone I treatment, thoughlater reappearance of carboxylic acid resonances suggested thatsaponification of the esters may have occurred.

FIG. 16A displays the molar hydrogen/carbon ratio (H/C) of thestabilized bio-oil as function of TOS. The H/C ratio is corrected forthe presence of methanol and water. The H/C ratio was higher than thatof the reduced-inorganic bio-oil feed (1.1) but decreased with TOSsuggesting continued catalyst deactivation. Even after 1,000 h TOS, theH/C ratio was at 1.4, significantly higher than that of the feed,indicating that the catalyst was still active.

FIG. 16B displays the Total Acidity Number, TAN (mg KOH/gram of sample).The TAN was less than the feed stock even after 1,000 h TOS. However,the TAN increased with TOS reflecting deactivation of catalyst. The TANof the stabilized bio-oil was still lower than that of the feed after1,000 h TOS.

The results of this EXAMPLE indicate that Zone I processing effectivelyreduced aldehydes during over the 1,000 h TOS hydrotreatment operation.FIG. 16A shows that significant hydrogenation continued to occur,increasing the H/C ratio from 1.1 to 1.4, even at 1,000 h TOS. Moreover,FIG. 14 shows that the pH of the stabilized bio-oil was fairly constantat about 3.5, relative to the pH of 2.4 for the reduced-inorganicbio-oil feed. FIG. 16B shows that the TAN of the product is still lowerthan the TAN of the feed. Although there is some indication ofdeactivation of the catalyst, these results show that the catalyst wasstill effective at reducing the aldehydes in the reduced-inorganicbio-oil feed, in hydrogenation, and in reducing organic acids. Thestabilized bio-oil produced in this EXAMPLE was collected and reservedfor further use.

Example 11 Production of Hydrocarbon Products by HydrotreatingStabilized Bio-Oil

The stabilized bio-oil produced in EXAMPLE 10 was then treated in asecond stage, Zone II hydrotreatment/cracking process hydrotreatingusing a sulfided CoMo catalyst. This EXAMPLE was conducted at about 310°C. under about 1,500 PSI of hydrogen. Further runs are contemplated in atemperature range of 280-340° C. under about 1160-1740 PSI of hydrogen.

In an initial run, the Zone II process was run for 200 h TOS wassuccessfully finished in this quarter. FIG. 17A is a graph of thedensity of the hydrocarbon product of Zone II versus TOS. FIG. 17A showsthat the density of the hydrocarbon product of Zone II increased duringthe first 60 h TOS and then was relatively constant from 60-200 h TOS.FIG. 17B shows that H₂ consumption was also constant during the run.Further runs using this same catalyst and another stabilized bio-oilsample effectively demonstrated about 1,400 h TOS.

To the extent that the term “includes” or “including” is used in thespecification or the claims, it is intended to be inclusive in a mannersimilar to the term “comprising” as that term is interpreted whenemployed as a transitional word in a claim. Furthermore, to the extentthat the term “or” is employed (e.g., A or B) it is intended to mean “Aor B or both.” When the applicants intend to indicate “only A or B butnot both” then the term “only A or B but not both” will be employed.Thus, use of the term “or” herein is the inclusive, and not theexclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into”are used in the specification or the claims, it is intended toadditionally mean “on” or “onto.” To the extent that the term“selectively” is used in the specification or the claims, it is intendedto refer to a condition of a component wherein a user of the apparatusmay activate or deactivate the feature or function of the component asis necessary or desired in use of the apparatus. To the extent that theterms “operatively coupled” or “operatively connected” are used in thespecification or the claims, it is intended to mean that the identifiedcomponents are connected in a way to perform a designated function. Tothe extent that the term “substantially” is used in the specification orthe claims, it is intended to mean that the identified components havethe relation or qualities indicated with degree of error as would beacceptable in the subject industry.

As used in the specification and the claims, the singular forms “a,”“an,” and “the” include the plural unless the singular is expresslyspecified. For example, reference to “a compound” may include a mixtureof two or more compounds, as well as a single compound.

As used herein, the term “about” in conjunction with a number isintended to include ±10% of the number. In other words, “about 10” maymean from 9 to 11.

As used herein, the terms “optional” and “optionally” mean that thesubsequently described circumstance may or may not occur, so that thedescription includes instances where the circumstance occurs andinstances where it does not.

As stated above, while the present application has been illustrated bythe description of embodiments thereof, and while the embodiments havebeen described in considerable detail, it is not the intention of theapplicants to restrict or in any way limit the scope of the appendedclaims to such detail. Additional advantages and modifications willreadily appear to those skilled in the art, having the benefit of thepresent application. Therefore, the application, in its broader aspects,is not limited to the specific details, illustrative examples shown, orany apparatus referred to. Departures may be made from such details,examples, and apparatuses without departing from the spirit or scope ofthe general inventive concept.

The various aspects and embodiments disclosed herein are for purposes ofillustration and are not intended to be limiting, with the true scopeand spirit being indicated by the following claims.

1. A method 200 for forming a stabilized bio-oil suitable for subsequenthydrotreatment, comprising: 202 providing the bio-oil; 204 filtering thebio-oil effective to remove at least a portion of particles having aneffective particulate diameter greater than about 10 micrometers; 206treating the bio-oil effective to remove at least a portion of inorganicspecies from the bio-oil; and 208 catalytically stabilizing the bio-oil,thereby providing the stabilized bio-oil suitable for subsequenthydrotreatment.
 2. The method of claim 1, providing the bio-oilcomprising pyrolyzing biomass to produce the bio-oil in a downflowreactor.
 3. The method of claim 1: providing the bio-oil comprisingpyrolyzing the biomass in a downflow reactor to produce a bio-oil vapor;and filtering the bio-oil comprising in-line filtering the bio-oil vaporproduced by the pyrolysis effective to remove at least a portion of theparticles having the effective particulate diameter greater than about10 micrometers.
 4. The method of claim 1, filtering the bio-oilcomprising: a first filtering process effective to remove at least aportion of the particles having an effective particulate diametergreater than about 10 micrometers; and a second filtering processeffective to remove at least a portion of the particles having aneffective particulate diameter in micrometers greater than one or moreof about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3,0.2, and 0.1.
 5. The method of claim 4, the second filtering processconducted using one or more of: a pressure differential in pounds persquare inch of at least about one or more of: 5, 10, 15, 20, 30, 40, 50,60, 70, 80, 90, 100, 125, 150, 175, and 200; and a temperature in ° C.of at least about one or more of: 30, 40, 50, 60, 70, 80, 90, and 100.6. The method of claim 1, treating the bio-oil effective to remove atleast a portion of inorganic species from the bio-oil comprisingcontacting the bio-oil to one or more of: an ion exchange resin, azeolite, and activated carbon.
 7. The method of claim 1, treating thebio-oil effective to remove at least a portion of inorganic species fromthe bio-oil comprising reducing the amount of one or more inorganicspecies in the bio-oil to a concentration in parts per million of lessthan one or more of about: 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2,and
 1. 8. The method of claim 1, catalytically stabilizing the bio-oilcomprising contacting the bio-oil to a stabilizing catalyst comprising ametal dispersed on a solid support.
 9. The method of claim 1, furthercomprising: contacting the bio-oil to a diluting medium to form adiluted bio-oil, and catalytically stabilizing the bio-oil comprisingcontacting the diluted bio-oil to a stabilizing catalyst.
 10. The methodof claim 9, the diluting medium comprising one or more of: an organicsolvent, a petroleum fuel, water, and a portion of the stabilizedbio-oil.
 11. The method of claim 10, further comprising removing atleast a portion of the solvent comprising one or more of: the organicsolvent, the petroleum fuel, and the water from the diluted bio-oilafter catalytically stabilizing the diluted bio-oil.
 12. The method ofclaim 1, catalytically stabilizing the bio-oil comprising contacting thebio-oil to a stabilizing catalyst comprising a zeolite.
 13. The methodof claim 1, catalytically stabilizing the bio-oil comprising contactingthe bio-oil to a stabilizing catalyst under conditions comprising one ormore of: a temperature in ° C. of about one or more of: 40 to 300, 100to 280, 120 to 270, 130 to 250, 140 to 225, 150 to 200, 160 to 180, and170; a pressure in PSI of about one or more of: 500 to 2500, 750 to2250, 1000 to 2000, 1250 to 1750, 1400 to 1600, and 1500; and a presenceof hydrogen.
 14. The method of claim 1, catalytically stabilizing thebio-oil comprising one or more of: flowing the bio-oil past astabilizing catalyst at a liquid hourly space velocity (LHSV) of betweenabout 0.05 hr⁻¹ to 1 hr⁻¹; and contacting the bio-oil to the stabilizingcatalyst for a Time On Stream (TOS) in hours of at least about one ormore of: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1,100, 1,200,1,300, 1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000,8,000, 12,000, and 16,000.
 15. The method of claim 1, catalyticallystabilizing the bio-oil comprising flowing the bio-oil past astabilizing catalyst, the method further comprising regenerating thestabilizing catalyst, comprising one or more of: rinsing the stabilizingcatalyst with an organic solvent; and contacting the stabilizingcatalyst with hydrogen at a temperature in ° C. of about one or more of:250 to 550, 300 to 500, 325 to 475, 350 to 450, 375 to 425, and
 400. 16.The method of claim 1, comprising filtering the bio-oil effective toremove at least a portion of particles having an effective particulatediameter greater than about 1 micrometer.
 17. A method 350 for forming ahydrocarbon product from a bio-oil, comprising: 352 providing thebio-oil; 354 filtering the bio-oil effective to remove at least aportion of particles having an effective particulate diameter greaterthan about 10 micrometers; 356 treating the bio-oil effective to removeat least a portion of inorganic species from the bio-oil; 358catalytically stabilizing the bio-oil to provide a stabilized bio-oil;and 360 hydrotreating the stabilized bio-oil comprising contacting thestabilized bio-oil to a hydrotreatment catalyst in the presence ofhydrogen, thereby providing the hydrocarbon product.
 18. The method ofclaim 17, the hydrotreatment catalyst comprising one or more of: anactive metal catalyst and a sulfided catalyst.
 19. The method of claim17, hydrotreating the stabilized bio-oil comprising contacting thestabilized bio-oil to a hydrotreatment catalyst in the presence of asubstantial excess of hydrogen at a pressure in pounds per square inchgauge of one or more of: 100 to 2000, 500 to 1800, and 1000 to
 1500. 20.The method of claim 17, hydrotreating the stabilized bio-oil comprisingcontacting the stabilized bio-oil to the hydrotreatment catalyst underconditions comprising one or more of: a liquid hourly space velocity(LHSV) of between about 0.05 hr⁻¹ to 1 hr⁻¹; and in the presence ofhydrogen for a Time On Stream (TOS) in hours of at least about one ormore of: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1,100, 1,200,1,300, and 1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000, 6,000,7,000, 8,000, 12,000, and 16,000.
 21. The method of claim 17, comprisingfiltering the bio-oil effective to remove at least a portion ofparticles having an effective particulate diameter greater than about 1micrometer.